3.18 Nitriles: General Methods and Aliphatic Nitriles, Pages 611-640, Michael
North
3.19 α,β-Unsaturated and Aryl Nitriles, Pages 641-676, Milton J. Kiefel
and
STEWART K. RICHARDSON
University of Notre Dame, IN, USA
2[90[0 SATURATED UNSUBSTITUTED ALDEHYDES 1
2[90[0[0 From Alkanes 1
2[90[0[1 From Alkenes 1
2[90[0[2 From Alkynes 2
2[90[0[3 From Halides 2
2[90[0[4 From Alcohols and their Derivatives 2
2[90[0[4[0 By oxidation of primary alcohols 2
2[90[0[4[1 From diols 6
2[90[0[4[2 Oxidation of alcohol derivatives 7
2[90[0[4[3 Rearran`ement of allylic alcohols 7
2[90[0[5 From Epoxides 8
2[90[0[6 From Acetals\ Enol Ethers and Enol Esters 8
2[90[0[7 From Aldehydes or Ketones 09
2[90[0[7[0 From saturated aldehydes or ketones 09
2[90[0[7[1 From unsaturated aldehydes 01
2[90[0[7[2 From a!functionalized aldehydes 01
2[90[0[8 From Carboxylic Acids and their Derivatives 02
2[90[0[8[0 Reaction of carbon nucleophiles with acids and their derivatives 02
2[90[0[8[1 Formylation reactions 03
2[90[0[8[2 Other preparations from acids and acid derivatives 04
2[90[0[09 From Sulfur!containin` or Other Lower!Chalco`en!Containin` Precursors 04
2[90[0[00 From Nitro`en!containin` Precursors 06
2[90[0[00[0 From amines 06
2[90[0[00[1 From oximes\ hydrazones and their derivatives 07
2[90[0[00[2 From nitroalkanes 07
2[90[0[01 From Or`anosilanes 07
2[90[0[02 From Or`anoboranes 08
2[90[0[03 Methods Involvin` Umpolun` 08
2[90[0[03[0 Formyl anion equivalents 19
2[90[0[03[1 Other anion equivalents 19
0
1 Alkyl Aldehydes
2[90[1[3 Alkynyl!Substituted Alkyl Aldehydes 14
2[90[1[3[0 Fra`mentation reactions 14
2[90[2 HALOALKYL ALDEHYDES "a\ b AND MORE REMOTE HALOGEN# 15
2[90[2[0 Introduction 15
2[90[2[1 From Stable Enol Derivatives and Enamines 15
2[90[2[2 From Aldehydes 15
2[90[2[3 Miscellaneous Preparations 16
2[90[2[3[0 Functional `roup transformations 16
2[90[2[3[1 Carbon0carbon bond!formin` methods 16
2[90[3 ALDEHYDES BEARING AN OXYGEN FUNCTION 17
2[90[3[0 OH!functionalized Aldehydes 17
2[90[3[0[0 a!OH!functionalized aldehydes 17
2[90[3[0[1 b! and more remotely functionalized OH aldehydes 20
2[90[3[1 OR!functionalized Aldehydes 20
2[90[3[2 OX!functionalized Aldehydes 22
2[90[4 ALDEHYDES BEARING A SULFUR FUNCTION 23
2[90[4[0 SH! and SR!functionalized Aldehydes 23
2[90[4[1 Hi`her!coordinated Sulfur!functionalized Aldehydes 26
2[90[5 ALDEHYDES BEARING A SELENIUM OR TELLURIUM FUNCTION 26
2[90[5[0 SeH!\ TeH!\ SeR! or TeR!functionalized Aldehydes 26
2[90[6 ALDEHYDES BEARING A NITROGEN FUNCTION 28
2[90[6[0 NH1!\ NHR! and NR1!functionalized Aldehydes 28
2[90[6[0[0 a!NH1!\ NHR! and NR1!functionalized aldehydes 28
2[90[6[0[1 b! and more remotely NH1!\ NHR! and NR1!functionalized aldehydes 33
2[90[6[1 NHX! and NX1!functionalized Aldehydes 35
2[90[6[2 NY!functionalized Aldehydes 35
2[90[7 ALDEHYDES BEARING A PHOSPHORUS\ ARSENIC\ ANTIMONY OR
BISMUTH FUNCTION 37
2[90[7[0 XR1\ X¦R2!functionalized Aldehydes 37
2[90[7[1 Hi`her!coordinated Phosphorus!\ Arsenic!\ Antimony! or Bismuth!functionalized Aldehydes 38
2[90[8 ALDEHYDES BEARING A METALLOID FUNCTION 40
2[90[8[0 Silicon!functionalized Aldehydes*a!silyl Aldehydes 40
2[90[8[0[0 From alcohols 40
2[90[8[0[1 From aldehydes or ketones 40
2[90[8[1 b!Silyl Aldehydes 41
78% ee
i, BHI•Me2S O O
Bun + (2)
ii, H2O2, OH– Bun Bun
99.0 : 1.0
OH O
TPAP
O O (4)
70%
O-TBDPS O-TBDPS
TBDPS = t-butyldiphenylsilyl
"d# Miscellaneous metal oxidants[ Although catalytic molybdenum! and tungsten!based systems
are well established for the oxidations of secondary alcohols\ primary alcohols are generally una}ec!
ted[ However\ two molybdenum peroxy complexes\ "0# ð79TL3732Ł and "1# ð76JOC4356Ł\ which are
both used stoichiometrically\ do oxidize primary alcohols to aldehydes[ Osmium tetroxide in ether
has the unusual selectivity of oxidizing primary alcohols in the presence of secondary alcohols\
although the high reactivity of the reagent to other functionalities limits the application of the
reaction ð73S844Ł[ Nickel"II# bromide catalyses the oxidation by benzoyl peroxide of primary
alcohols to aldehydes in high yield ð68JOC1844Ł[
A number of catalytic palladium systems for alcohol oxidation are known\ and the scope of the
method has been examined ð72JOC0175Ł[ The optimal conditions employ 0Ð2 mol) of either a
palladium"9# or palladium"II# catalyst with bromobenzene as a reoxidant[ The oxidation can
also be performed under phase transfer conditions with iodobenzene as a reoxidant ð74TL5146Ł[
5 Alkyl Aldehydes
O
O O
Mo
Ph O O O O
N O O O
Mo
O N
Ph O O
(1) (2)
Ytterbium"III# nitrate will catalyse the oxidation of alcohols by iodosobenzene[ Like osmium
tetroxide this reagent shows the unusual selectivity of oxidizing primary alcohols in preference to
secondary alcohols ð82CL460Ł[
AcO OAc F F
I OAc I F
O O
O
(3) (4)
Saturated Unsubstituted 6
"iv# Oppenauer and related oxidations
The oxidation of secondary alcohols by an aluminum alkoxide!catalysed hydrogen transfer to an
acceptor ketone\ present in excess to drive the equilibrium in the desired direction\ was _rst reported
by Oppenauer ð26RTC026Ł[ The method was quite widely used in the older literature\ particularly
for the oxidation of steroidal alcohols\ and was the subject of an early review ð40OR"5#196Ł[ Unfor!
tunately\ the method\ despite the mild conditions\ cannot be directly applied to the oxidation of
primary alcohols to aldehydes since the product aldehydes condense with the excess ketone present
as a hydrogen acceptor\ and until recently there was no general solution to this problem[ However\
new catalysts which do not catalyse the aldol side reaction are now becoming available[ These include
bis"cyclopentadienyl#zirconium hydride ð75JOC139\ 75S663Ł\ zirconium oxide with benzophenone as
the hydrogen acceptor ð80BCJ201Ł\ and a variety of lanthanide alkoxides ð73JOC1934Ł^ they make
the method an attractive option for the oxidation of sensitive substrates with the added bene_t of
avoiding any risk of overoxidation[
+
N Br–
O
(5)
"i# Ethers
A wide range of alkyl and silyl ethers of primary alcohols react with hydride!abstracting reagents
to give an oxonium ion which is hydrolysed to give the aldehyde on workup[ Thus\ methyl ethers
of primary alcohols are cleaved oxidatively by nitronium tetra~uoroborate ð66JOC2986Ł\ or uran!
ium"VI# ~uoride ð67JA4285Ł\ and O!trimethylsilyl derivatives of primary alcohols can be oxidized
with trityl tetra~uoroborate ð65JOC0368Ł[ Similarly\ sodium bromate\ in the presence of a catalytic
amount of cerium"IV# ammonium nitrate\ will oxidize a wide range of ether derivatives\ including
methyl\ benzyl\ trimethylsilyl and t!butyldimethylsilyl ð79S786Ł[
Trimethylsilyl ethers can be oxidized using DMSO:oxalyl chloride\ although the conditions
"−29>C for 29Ð34 minutes# are appreciably more vigorous than are normally required for alcohol
oxidations ð76JCS"P0#0110Ł[ t!Butyldimethylsilyl ethers are inert to the reaction conditions\ and
hindered or secondary trimethylsilyl ethers react appreciably less rapidly\ allowing some interesting
selective oxidations to be achieved "Equation "4## ð78S839Ł[ The oxidative deprotection and stability
under alcohol oxidative conditions of silyl ethers has been the subject of a very comprehensive
review\ which includes some useful tabulations of the reactivities observed ð82S00Ł[
O O
O DMSO, (COCl)2 O
(5)
O-TMS 62% O
OSiEt3 OSiEt3
"ii# Esters
Aldehydes may be prepared under strictly neutral conditions by the photolysis of the pyruvate
esters of primary alcohols ð65JOC2929\ 65SC170Ł\ and the reaction has been applied to good e}ect in
the preparation of a number of delicate carbohydrate aldehydes ð66JOC0105Ł[ Alkyl nitrites are
oxidized in a Kornblum!type reaction by DMSO ð75T3022Ł\ and alcohols can be oxidized via their
aci!nitro esters in a reaction that is probably mechanistically related ð68CC292\ 70TL1184Ł[
OH O
LiNHCH2CH2NH2
(6)
74%
I–
I– O
TMS-I O-TMS O-TMS
O O O O+ +O + I
TMS
R
R R R
Scheme 1
09 Alkyl Aldehydes
O O O O
AcCl, ZnCl2
DMSO
MeO O (7)
O 63% O
OMe
Enol esters and silyl enol ethers are most often prepared from aldehydes as intermediates in
other reactions[ They are\ in general\ relatively labile compounds hydrolytically\ making their
transformations back to aldehydes relatively straightforward should it be required[ Tributyltin
~uoride has been recommended for the hydrolysis of more stable silyl enol ethers ð72JA4692Ł[
Ph Ph
Scheme 2
Although the reaction of silyl enol ethers derived from ketones with tertiary alkylating agents
under Lewis acid catalysis to give\ after workup\ good yields of alkylated ketone is well established\
examples with aldehyde!derived silyl enol ethers are uncommon ð71AG"E#85Ł[ The reaction is impor!
tant in that it complements enolate chemistry both in using acidic rather than basic conditions and\
most importantly\ by allowing the introduction of tertiary alkyl groups[
"ii# Homolo`ation
Although any preparation of functionalized aldehydes involving carbon0carbon bond formation
and starting from a ketone or aldehyde can be thought of as a homologation\ this section will only
Saturated Unsubstituted 00
deal with reactions which increase the number of carbon atoms without any increase in the functional
group complexity of the molecule[
Homologation of aldehydes generally involves alkenation to give a functionalized alkene which
can be converted into the required aldehyde in a second step "Scheme 2 and Table 0#[ The reagents
can often also be applied to the preparation of aldehydes from ketones\ and use a wide range of
alkenation methodologies\ including Wittig and related phosphorus chemistry\ and Peterson reac!
tions[ A variety of enol ether and enamine precursors to homologated aldehydes can also be prepared
via the diazoalkene derivative resulting from the reaction of an aldehyde or ketone with dimethyl
diazomethylphosphonate "Scheme 3# ð72JOC337Ł[
R O X O
R R
Scheme 3
N2
OMe
O •
(MeO)2P(O)CHN2
Scheme 4
Corey et al[ have developed a variant of the Peterson strategy in which the carbon atom is
introduced by cyanohydrin formation\ which\ although employing several steps\ is useful for the
preparation of aldehydes from very hindered ketones ð79JA0631Ł[ A very di}erent homologative
approach to aldehydes\ which also introduces the carbon atom at the acid oxidation level\ uses the
dithiolane containing WadsworthÐEmmons reagent "5# and involves the borohydride reduction of
a ketene thioacetal intermediate "Scheme 4# ð76S68Ł[
O
S S
HBF4
–
+ (MeO)2P(O)
100%
S S
(6)
CHO
S 98% S 90%
BF4–
Scheme 5
01 Alkyl Aldehydes
2[90[0[7[1 From unsaturated aldehydes
Me
N Ph
N X
Me
(7)
Saturated Unsubstituted 02
2[90[0[8 From Carboxylic Acids and their Derivatives
O O O O
EtOTf, L-selectride
(8)
MeO NMe2 69% MeO
Perhaps surprisingly\ carboxylic acids themselves may be directly reduced to aldehydes with
a variety of reagents[ These include the thexyl chloroboraneÐdimethyl sul_de complex\ which is
incompatible with alkene functionality ð76JOC4399Ł\ and the thexyl bromoboraneÐdimethyl sul_de
complex\ which although compatible with alkenes requires dimethyl sul_de as the solvent ð76JOC4929\
76TL1278Ł[ In neither case is the workup particularly straightforward[ Probably more convenient is
bis"N!methylpiperazinyl#aluminum hydride\ which may be prepared as a stock solution in THF\
03 Alkyl Aldehydes
O S
R N S
(8)
and e}ects the reduction in high yield ð73JOC1168Ł[ The pentavalent silane "8# has also been used
for this reduction ð76TL2830Ł[ Despite this range of reagents\ in practice carboxylic acids are most
often reduced to aldehydes in multistep sequences\ either via the primary alcohol or a heterocyclic
derivative such as a benzimidazoles "Scheme 5# ð70S292Ł[
Ph H
Si H
NMe2
(9)
N
O NH2 i, NaOEt
polyphosphoric acid ii, MeI
OH
+ N O
70% iii, NaBH4
O NH2 H 89%
Me
N HCl O
O
66%
N O
Me
Scheme 6
(10)
Probably the most widely used formylating reagent for Grignard reagents after DMF is triethyl
orthoformate\ although comparative studies suggest that higher yields are obtained if the cyclic
orthoester "00# is used ð79JCS"P0#645Ł[ Other formates have not been widely exploited as formylating
agents\ although both methyl formate and sodium or lithium formates can be used to formylate
Saturated Unsubstituted 04
organometallic reagents[ The former reagent requires very low temperatures "−009>C# if secondary
alcohol formation is to be avoided in its reaction with alkyllithium reagents ð75JOC840Ł\ whereas
the latter requires elevated temperatures if a reasonable rate of reaction with Grignard reagents is
to be obtained ð73TL0732Ł[
O
O
O O OMe
(11)
Several procedures are available in which the formyl group derives ultimately from carbon
monoxide[ The carbon monoxide can either be gaseous\ as in the reaction of tetraalkylstannanes
with carbon monoxide under palladium"II# catalysis ð68TL1590Ł\ or in the form of a metal carbonyl
as in the protonation of acyl ferrates prepared from the reaction of Grignard reagents with pen!
tacarbonyliron ð71BCJ0552Ł[ The latter method may be used to prepare 0!deuteroaldehydes if deut!
eroacetic acid is used to decompose the intermediate[ 0\2!Benzodithiolium tetra~uoroborate "01#
has also been reported as a useful synthon for the preparation of deutereoaldehydes ð71BCJ1178Ł[
S
+
D
S
(12)
i, LiTMP, CH2Br2
OMe ii, BunLi OMe OLi
CO2Me
i, TMS-Cl
OMe ii, H3O+ OMe
OLi 61% CHO
Scheme 7
SR1
R2 +SR1
SR1 –R1S– H2O O
R2 R2
SR1 +H+
R2
Scheme 8
The Pummerer reaction allows the preparation of an a!functionalized sul_de from a sulfoxide
bearing at least one a hydrogen atom\ in an internal redox process that results in the reduction of
the sulfoxide with concomitant oxidation of a neighbouring carbon atom from the alcohol to the
aldehyde oxidation state ð80OR"39#046Ł[ The reaction provides an important approach to aldehydes
from alkyl aryl sul_des since the product a!functionalized sul_des can be readily hydrolysed to the
aldehydes "Scheme 8# ð67S770Ł[ a!Silyl sulfoxides\ prepared by silylation of sulfoxide!stabilized
anions\ spontaneously undergo a Pummerer rearrangement at room temperature to give a!silyloxy
sul_des\ which can be hydrolysed to the required aldehyde under very mild conditions ð64TL1906Ł[
Related aldehyde precursors\ a!chlorosul_des\ can be prepared by NCS chlorination of sul_des\
and are hydrolysed in the presence of mercury"II# or cadmium"II# salts ð65SC464Ł[ The chlorination
and hydrolysis can alternatively be achieved in the same pot by sequential treatment of a sul_de
with sulfuryl chloride and silica gel ð72JOC2460Ł[
OTf O
TFAA NaHCO3
BnO BnO BnO
SOPh 2,6-lutidine SPh 53%
Scheme 9
Scheme 10
+ + dbu
Bun NH2 + Me N CHO Me N
PhSO2– N
Bun
+
Me N H3O+
BunCHO
N 84%
Bun
Scheme 11
Although the ease of hydrolysis of imines makes them a particularly attractive intermediate in an
amine to aldehyde conversion\ a recent method which involves the oxidation of a metallated
silylamine with dry air to give an oxime appears attractive[ The oxime intermediate is hydrolysed
to the required aldehyde during ~ash chromatographic puri_cation\ and the conditions are com!
patible with phosphine\ thioether and tertiary amine functionalities "Scheme 01# ð77TL5690Ł[
OLi
TMS TMS O O
HN N N
i, BunLi
OH
N O
SiO2, H2O
87%
Scheme 12
07 Alkyl Aldehydes
2[90[0[00[1 From oximes\ hydrazones and their derivatives
Probably because they are relatively stable derivatives of aldehydes\ and have the reputation of
only being hydrolysed under fairly vigorous conditions\ oximes and hydrazones are relatively
infrequently considered as potential precursors or protecting groups\ despite the very sizeable body
of literature describing methods of achieving this sort of transformation[
Classical oxime and hydrazone hydrolyses use fairly vigorous acidic conditions^ however\ the
transformation can be achieved with milder heterogeneous acid catalysts such as Amberlyst!04 resin
for tosylhydrazones\ dinitrophenylhydrazones and semicarbazones ð77JCS"P0#1452Ł or Dowex!49
resin for oximes and semicarbazones ð77JOC767Ł[ Dimethylhydrazones may also be hydrolysed by
a Lewis acid!catalysed transfer of the hydrazine to acetone ð65S345Ł[ One important method of
facilitating the C1N hydrolysis of hydrazones is by metal complexation of the nitrogen to activate
the carbon atom to attack by water[ The metal ion most commonly used for this purpose is
copper"II#\ which also has the advantage of driving the reaction to completion by scavaging the
liberated hydrazine derivative ð65TL2556Ł[
Probably the largest group of methods for preparing carbonyl compounds from C1N derivatives
are those employing oxidizing agents[ These include nitrosating reagents\ which\ like the copper"II#
complexation\ work by activating the carbon atom to attack by water by removing electrons from
nitrogen[ An example of this type of method is the hydrolysis of oximes mediated by a mixture of
sodium nitrite and chlorotrimethylsilane which provides an in situ source of nitrosyl chloride
ð89TL5566Ł[ Active oxygen reagents can also be used[ For instance\ aryl hydrazones have been
cleaved with basic hydrogen peroxide ð67S808Ł\ and the recently introduced magnesium mon!
operoxyphthalate has been found to be particularly valuable in cleaving hydrazones without a}ect!
ing the stereochemical integrity of a chiral centre a to the aldehyde product ð89SL614Ł[
Dimethylhydrazones have also been regenerated with bu}ered periodic acid ð65TL2Ł[
Conventional high!valent metal oxidants can also be employed in the preparation of aldehydes
from oximes or hydrazones[ Thus\ bis"trimethylsilyl#chromate has been found valuable for the
preparation of aldehydes from oximes ð81SC1314Ł\ and thallium"III# acetate can be used to regenerate
aldehyde tosyl hydrazones ð68TL3472Ł[ Benzeneseleninic anhydride will also cleave a range of
C1N derivatives\ including oximes\ aryl and tosyl hydrazones\ and semicarbazones\ but not N\N!
dimethylhydrazones or O!methyl oximes[ The reagent appears to be particularly e}ective for the
regeneration of hindered substrates ð79JCS"P0#0101Ł[
Although the majority of new publications describe the use of oxidative reagents\ it is also possible
to achieve the transformation under reducing conditions^ for example\ both Raney nickelÐsodium
hypophosphite ð75SC792Ł and vanadium"II# chloride ð79S119Ł can be used for deoximation[ Despite
the variety in types of reducing agent used\ they all appear to involve an initial reduction to an
imine\ which is hydrolysed under either the reaction or workup conditions[
Lastly\ it has recently been reported that both oximes ð80JCS"P0#1945Ł and hydrazones ð80TL1546Ł
can be cleaved enzymatically with baker|s yeast[ The hydrolysis\ which is greatly aided by sonication\
gives near!quantitative yields of the aldehyde[
HO OH O
TFA
(9)
TBDMS 86% TBDMS
Aldehydes have also been prepared by the catalytic hydrogenation of acyl silanes containing a
phenyl group bound to silicon ð80TL346Ł[ Remarkably\ the reaction can be performed in the presence
of other hydrogenolizable functionalities\ such as benzyl and benzyloxymethyl ethers\ and acid!
sensitive groups such as t!butyldimethylsilyl and methoxymethyl ethers "Equation "09##[
O H2, Pd (cat.) O
O O
PhMe2Si (10)
82%
O OBn O OBn
OH
n-C6H13 O
Scheme 13
– i, BF3•OEt2
Br i, BunLi
Bu3B ii, H3O+ Bu
Scheme 14
The largest remaining group of d0 formyl synthons used for simple alkyl aldehyde preparations
are those based on nucleophilic metal carbonyl derivatives[ The best known example of these is the
Collman reagent Na1Fe"CO#3\ which reacts with primary and secondary halides and sulfonates to
give an alkyl iron complex which rearranges to the acyl complex in the presence of carbon monoxide
or a phosphine[ Treatment of the acyl complex with mineral acid then liberates the aldehyde
"Equation "00##[ The reagent tolerates ketone\ ester or nitrile functionalities\ but has the drawback
of being somewhat basic\ causing elimination of some substrates\ in particular tertiary halides and
sulfonates ð64ACR231Ł[ A number of related ionic iron carbonyl complexes ð78TL5260Ł\ including
polymer!supported variants ð67JOC0487Ł\ can also be used[ A quite remarkable formylation of an
alkyl acetate involves its treatment with octacarbonyldicobalt in the presence of a trialkylsilane[
The immediate product is a silyl enol ether which can either be isolated\ or hydrolysed with potassium
~uoride in methanol "Scheme 04# ð72JA0269Ł[
i, Na2Fe(CO)4, THF, CO
ii, HOAc
Br CHO (11)
Cl Cl
82%
MeEt2SiH, Co2(CO)8
OAc
CO, 200 °C OSiEt2Me KF
63% 100%
But But
But
Scheme 15
The d0 reactivity of cyanohydrins that underlies the benzoin condensation has also inspired a
number of formyl anion synthons such as the N\N!diethylaminoacetonitrile anion "Et1NCHCN#\
which\ after alkylation\ is hydrolysed with oxalic acid in aqueous THF to give the required aldehyde
ð67TL4064Ł[
Scheme 16
11 Alkyl Aldehydes
O O
Pd-C, ∆
(12)
58%
O O
Br
Br2, oxirane, –80 °C ButOK, 18-crown-6 190 °C
O O
81% 93% 77%
Br
O
Scheme 17
O
∆
(13)
O
O
OH
220 °C
(14)
90%
The preparation of the appropriate starting material for an oxy!Cope rearrangement is not always
trivial[ One particularly ingenious way of overcoming this problem is to use a tandem ð1\2Ł WittigÐ
oxy!Cope rearrangement of a diallyl ether ð71CL0238Ł[ Unfortunately\ studies of this chemistry with
chiral cyclohexenyl systems have shown that the ð0\1Ł Wittig rearrangement\ which leads to the
enantiomeric product\ competes to a minor extent with the ð1\2Ł rearrangement "Scheme 07#
ð71TL2820Ł[
OH OH
O
BunLi BunLi
[1,2]Wittig [2,3]Wittig
O O
minor major
Scheme 18
b and More Remotely Unsaturated 12
2[90[1[0[2 Other preparations
i, CO
ZrCp2HCl ii, H3O+ O
Zr
80–90% Cl 98%
Scheme 19
Scheme 20
Me3SnCl
MgBr + ZnBr
n-C6H11 MgBr
n-C6H11
ZnBr
Scheme 21
13 Alkyl Aldehydes
2[90[1[1 Alkyl Aldehydes with More than One Double Bond
Aldehydes containing more than one nonconjugated double bond are generally prepared by
methods that are directly analogous to those used for the preparation of saturated aldehydes "see
Section 2[90[0# or aldehydes with a single nonconjugated double bond "see Section 2[90[1[0#[
The oxy!Cope rearrangement\ a powerful approach to d\o!unsaturated aldehydes and ketones
"see Sections 2[90[1[0[1 and 2[92[1[0[1#\ has been extended by several workers to give compounds
with two or more double bonds[ So far these variants have been applied only to unsaturated
ketone preparations "see Section 2[92[1[1#\ although in view of the success of the basic oxy!Cope
rearrangement for the preparation of aldehydes\ there seems to be no obvious chemical reason for
this limitation[
N
CHO
N AlCl3, ∆ 6N HCl Et
+ Et
40%
Cl
Et
Scheme 22
O O O
B Pd(PPh3)4 H3O+
+ OEt
3 96%
Br OEt O
Scheme 23
Cl Cl O Cl
I H2CCHCONH2 i, NaOCl, MeOH O
Pd0, NaOAc, 100 °C NH2 ii, H3O+
87% 38%
Cl Cl Cl
Scheme 24
I
10 Pd0
+ 1 OH
11 91%
11 1 10 1 O
O
+ (16)
88 : 12
Ph Ph i, KNPri2, Et2O
OMe NaH, cinnamyl bromide OMe ii, BunI
90% 65%
OH O Ph
(15)
Ph
OMe Bun
HClO4
+ (15)
O Bun O Ph
75% ee
Ph
Scheme 25
O + (17)
42% CHO
SO2NHNH2
Ph
N Ph
N
140 °C
O (18)
61% CHO
2[90[2[0 Introduction
The literature to mid!0875 on the synthesis and chemistry of a!halo aldehydes containing one or
two halogen atoms has been the subject of an excellent chapter by De Kimpe and Verhe in one of
the Updates to the Chemistry of the Functional Groups monographs edited by Patai and Rappoport
ðB!77MI 290!90Ł[
a!Halo aldehydes are considerably more reactive than are a!halo ketones\ and satisfactory general
methods for their preparation have only become available since the mid!0859|s[ Their isolation and
use can also be di.cult because of the frequently high stability of many of their hydrates\ and the
ease with which they can oligomerize[ One recently reported solution to the problem involves the
preparation of an aldehydeÐLewis acid complex by treatment of the oligomer with methylaluminum
bis"1\5!diphenylphenoxide#[ The resulting complex can then be employed directly in reactions with
nucleophiles ð82JA2832Ł[ Because of these di.culties\ the literature is considerably more sparse than
for a!halo ketones\ and this discussion is arranged by starting material rather than by halogen[
More remotely substituted halo aldehydes are generally prepared by methods typical of unfunc!
tionalized aldehydes or halo compounds\ and few general methods speci_cally aimed at this class
of compounds have been reported[
F
O-TMS O
F2/N2, CFCl3, –78 °C
(19)
72%
The literature on the preparation of a!iodo aldehydes is particularly sparse\ although several very
satisfactory synthetic approaches have been described[ These include iodination of aldehydes by
iodine in the presence of mercury"II# chloride ð75S567Ł\ of aldehyde enolates with iodine ð68TL1706Ł\
and the halogen exchange of a!chloroaldehydes with sodium iodide in dry acetonitrile ð75OPP68Ł[
a\a!Dihalo aldehydes can be prepared from aldehydes by reaction with either chlorine or bromine
in the presence of pyrrolidine hydrohalide salt as a catalyst ð74SC866Ł[
F F
SPh dibal-H O
n-C8H17 n-C8H17
92%
OAc
dibal-H = diisobutylaluminum hydride
Scheme 26
The preparation of a\a!dichloro aldehydes from primary alcohols with chlorine in a dimethyl!
formamideÐchloroformÐmagnesium chloride system has been reported to give better results than
previously described conditions ð77BSB414Ł[
a!Bromo aldehydes can be prepared by the haloboration of terminal alkynes[ The reaction\ which
is compatible with halide ester and alkene functionalities\ involves a modi_ed alkaline peroxide
oxidative workup designed to reduce the base!catalysed elimination of hydrogen bromide from the
product "Scheme 16# ð74S395Ł[
Br
O
Scheme 27
a dihalomethyllithium with a ketone[ The reaction\ which involves an a!halo epoxide intermediate\
appears to be fairly general for cyclic ketones and can be applied to quite sensitive structures\ such
as protected sugars "Equation "19## ð80CL0358\ 82JOC4382Ł[ a!Chloro and a!bromo aldehydes can
also be prepared by the formylation of the related a!haloalkyllithium reagents\ which are prepared
by metal halogen exchange of 0\0!dihaloalkanes at −099>C\ with methyl formate "Equation "10##
ð79S533Ł[
i, BunLi i, NaBH4 O
N ii, RBr N ii, H3O+ R
X X
O O X
(18) R
X = F, Cl
Scheme 28
O i, Cl2CHLi O
O ii, NaOAc, 15-crown-5 O
O O O O (20)
77%
Cl
O O O
O
i, LDA, –100 °C
Br ii, HCO2Me
Br
Bun Bun (21)
Br 73% CHO
N
N
N
N
(19)
Scheme 29
S
TMS + O NBOC O NBOC
85%, de 92%
N S
CHO
HO N
S NHBOC BOCNH S
TMS + BnO BnO
60%, de 80% N
N CHO
OH
Scheme 30
Very few methods are available for the asymmetric addition of formyl anions to achiral aldehydes\
but one successful approach uses the enolate derived from the racemic iron complex "19#[ The
copper enolate gives predominantly the RRS "SSR# adduct\ whereas the aluminum enolate is
selective\ at least 3 ] 0\ for the RRR "SSS# isomer "Equation "11##[ In an attempt to obtain homochiral
materials\ the menthyl complexes were prepared\ and the two diastereoisomers readily separated by
column chromatography[ The "R# isomer "10#\ via its aluminum enolate\ reacts with iso!
butyraldehyde to give preferentially the "RRR# adduct in a 04 ] 0 excess[ Under the same conditions
the "S# enantiomer gives a complex mixture of all four diastereoisomers\ indicating\ in this case\ a
mismatched stereochemical in~uence ð78TL1860Ł[ Epoxy sulfones\ for example "11#\ prepared via a
Darzens reaction between a chlorosulfone and a ketone\ undergo base!catalysed ring opening to
hydroxy aldehydes[ A list of references for much of the early work on the preparation of oxygenated
aldehydes has been published in this same paper ð73JOC0267Ł[
29 Alkyl Aldehydes
Ph Ph
OC
P
Fe
O OBn
(20)
Ph Ph
OC i, BunLi, –78 °C OBn
P ii, Et2AlCl, –40 °C
Fe R (22)
OBn
iii, RCHO, –100 °C
iv, Br2, BnOH OH
O OBn
O
Ph Ph
OC SO2Ph
P
Fe
O O-menthyl
THP-O
(21) (22)
Oxidative and reductive transformations can be used to prepare a!hydroxy aldehydes[ O!Silyl!
protected cyanohydrins can be reduced to a!hydroxy aldehydes using dibal ð80SL368Ł\ and optically
active hydroxy aldehydes ð83T1710Ł are available from the corresponding optically active cyano!
hydrins ð82SL796Ł[ A complementary reduction which gives carbonyl!protected hydroxy aldehydes
is the baker|s yeast!mediated reduction of cyclic and acyclic acyl dithioacetals to give\ usually\ the
"S#!alcohols in high enantiomeric excess ð89S0\ 80CRV38Ł[ In fact\ baker|s yeast!mediated reductions
can be used to establish a range of remote hydroxy carbonyl relationships\ although usually only
one enantiomer is available directly[ Both epimers of the same alcohol\ however\ can be prepared
from the stereocomplementary reduction of a ketone using the same chiral auxiliary "Equation "12##
ð81CL1062Ł[
S S S (23)
O O + O
O OH OH
Zn(BH4)2 99 : 1
NaBH4/YCl3 3 : 97
Nucleophilic attack of vinyl anions to carbonyl groups\ followed by ozonolysis of the alkene\
is a well!established method for the synthesis of a!hydroxy aldehydes\ and developments have
demonstrated that this method can be used to prepare homochiral products[ Addition of 0\1!
propadienyltributylstannane to aldehydes in the presence of a chiral borane has been shown to
occur with ×88) ee[ Protection of the alcohol and ozonolysis of the allene gives enantiomerically
pure products ð80TL4602Ł[ Alternatively\ optically pure acyl diene iron tricarbonyl complexes "12#
have been shown to give a single diastereoisomer of a tertiary alcohol on treatment with organo!
lithium reagents[ Exhaustive ozonolysis then gives the desired products "Scheme 20# ð89SL530Ł[
Terminal 0\1!diols can be oxidized selectively using catalytic Cp1ZrH1 at 049>C to give a!hydroxy
aldehydes ð75S663Ł[
O
R1 R1 i, H2O2, NaOH
R2Li, –78 °C R1
R2
O OH ii, O3, MeOH R2
OH
(CO)3Fe (CO)3Fe
(23)
Scheme 31
Bearin` an Oxy`en 20
2[90[3[0[1 b! and more remotely functionalized OH aldehydes
A well!established method for the synthesis of b!hydroxy aldehydes relies on the addition of allyl
organometallics to aldehydes\ followed by cleavage of the alkene with ozone[ A wide variety of
metals has been shown to promote the allylation\ and the high chemoselectivity and increasing ability
to predict and control the relative and absolute stereochemistry during the addition ð82CRV1196Ł has
allowed this to become a very powerful procedure for the synthesis of b!oxygenated aldehydes[ The
use of chiral catalysts with achiral aldehydes and ketones has been shown to give homoallylic alcohols
in excellent enantiomeric excess ð82JA6990\ 82JA7356\ 82JOC5432Ł[ Many formyl anion equivalents will
successfully attack epoxides to give b!hydroxy aldehydes\ and this method has been highlighted in
several reviews ðB!76MI 290!90\ 78T6532Ł[
Apparently few methods exist for the oxidation of 0\2!diols to 2!hydroxy aldehydes\ perhaps
due to the facile dehydration of the product[ However\ one method which is successful uses
N!oxoammonium salts ð89JOC351Ł\ and the yields are very high[ In the oxidation of 0\3! and 0\4!
diols the intermediate hydroxy aldehydes often undergo further in situ oxidation to the cor!
responding lactones[ As might be expected\ more remote hydroxy aldehydes can be successfully
isolated ð78JOC1869Ł[
The selective reduction of ketones in the presence of aldehydes is di.cult without a prior
protection step[ However\ the greater reactivity of the latter can be exploited using speci_c
conditions\ where protection occurs in situ[ Among the conditions developed to achieve this are
NaBH3:CeCl2 ð70TL3966Ł and LiAl"OBut#2H:ButNH1 ð71T0716Ł[
Homoenolate anions derived from protected aldehydes can add to other carbonyl groups to give
hydroxy aldehydes[ The reagents that have been developed for this purpose include "13#\ which
reacts with aldehydes\ ketones and a!silyloxy ketones leading to hydroxy or dihydroxy aldehydes
ð81JOC649\ 82T3812Ł\ "14#\ prepared from reductive lithiation of the corresponding sul_des ð81JOC5Ł\
and "15# ð83T2326Ł[ The development of other nucleophilic three!carbon homologating agents\
including homoenolate anions\ has been covered in an early review ð73CRV398Ł[
Li R2
Li
O O Li
OEt
O O R1
(24) (25) (26)
R CHO
NaIO4, MeOH O
O (24)
75–85% CHO
O R
O
Direct oxidation of aldehydes or their enol derivatives to the corresponding a!oxygenated deriva!
tives is less facile than for the corresponding ketones\ at least in part because of the greater reactivity
of aldehyde enolates[ However\ some methods have been applied to this transformation\ including
the use of mcpba ð64JOC2316Ł and lead tetraacetate ð72T750Ł to give a!acyloxy aldehydes\ and SAMP
21 Alkyl Aldehydes
or RAMP hydrazones to give a!alkoxy aldehydes ð77TL1326Ł[ The oxidative transformation of a
sulfoxide to an aldehyde\ via a Pummerer rearrangement\ has been known for many years ð67S770Ł\
and the mild conditions allow it to be used for the synthesis of functionalized aldehydes "Scheme
21# ð82CC873Ł[ A method for the synthesis of a!alkoxy aldehydes which could have wide applicability
is shown in Scheme 22[ Thus\ diastereospeci_c hydroxylation of an Evans imide\ followed by amide
exchange\ protection and reduction\ gives the product in high overall yield ð81JA8323Ł[ b!Alkoxy
imides\ generated by an Evans aldol approach\ can be reduced to b!alkoxy aldehydes via a similar
procedure ð81JOC0956Ł[ The enolate formed from 1!acetylthiazole undergoes aldol reactions with a
range of aldehydes[ Reduction of the ketone\ protection of the resulting alcohol and unmasking of
the aldehyde gives anti 1\3!dioxygenated aldehydes ð78TL5952Ł[
OBn O OBn OBn
TFAA, pyridine CuCl, K2CO3
S S
Ar Ar CHO
F F OCOCF3 F
TFAA = trifluoroacetic anhydride
Scheme 32
O O O O
i, ii MeO iii, iv
O N N
80% 78%
Me OH PMB-O
Bn
i, NaHMDS, 2-(phenylsulfonyl)-3-phenyloxaziridine, –78 °C; ii, AlMe3, MeONHMe•HCl, 45 °C;
iii, NaH, p-MeOC6H4CH2Br, 0 °C; iv, dibal, –78 °C
Scheme 33
Nucleophilic displacement of the halide from a!halo aldimines or a!halo aldehydes by oxygen
nucleophiles is not always a predictable reaction whose outcome depends on the substrate and
the conditions used "for a review\ see ðB!77MI 290!90Ł#[ Alkoxides are frequently the least useful
nucleophiles\ but carboxylate salts can be used more successfully ð71JOC0090Ł[ A novel\ ~exible and
iterative procedure for the synthesis of polyhydroxy aldehydes involves electrochemical oxidation
of alkoxysilanes "Scheme 23# ð81JOC0210Ł[
OMe OMe v, vi
i, ii iii, iv
HO MeO2CO MeO2CO TMS
TMS OMe vii, viii
OH
BnO TMS
OMe
i, anodic oxidation, Et4NOTs, MeOH; ii, ClCO2Me, C5H5N; iii, H3O+; iv, Br2CH-TMS, CrCl2; v, LiAlH4;
vi, (+)-diisopropyl tartrate, Ti(OPri)4, ButO2H; vii, NaH, BnBr; viii, BF3•Et2O, MeOH
Scheme 34
O O
OEt OEt
OEt OEt
Scheme 35
O S
thiourea
OEt OEt (25)
100%
OEt OEt
H
OH N
PPh3
N3 OEt OEt (26)
40%
OEt OEt
OH O OH OH O
R1 OH transketolase R1 R1 OH
CHO + LiO C CHO + (27)
2
OH
R1 = SH, R2S, R3O, F, CN, Me 52–78%, >98% ee 72–82%
O-TBDMS
O (28)
CHO
Ph O-TBDMS 75–87%, 98% ee
Ph
OH O-TES
TES-OTf
O (29)
Ph Ph CHO
collidine
80%
α
Bun Me
O O
O
(27)
R S OH O O O O
HS NaSH Br NaSH S
HO S R R R R R
(28) (29)
Scheme 36
R CHO
O
AcS
S
(30) (31)
Bearin` a Sulfur 24
Direct sulfenylation of aldehydes or their derivatives is\ perhaps\ the most useful preparation of
a!sulfenyl aldehydes\ and a number of procedures have been developed to achieve this[ The lithium
enolates of alkyl aldehydes\ generated from the treatment of a silyl enol ether with methyl lithium\
react with sulfenyl chlorides to give the desired products in fair yield ð62TL4002Ł\ while potassium
enolates react with dialkyl or diaryl disul_des ð68TL1706Ł[ The latter method works best for aldehydes
with only one a proton[ Metalloenamines also undergo reaction with disul_des to give similar
products ð63TL2844Ł[ Enamines derived from a chiral amine lead to enantiomerically enriched a!
sulfenyl ketones ð76S048Ł[ Other papers have shown that enol ethers ð74T3338Ł and silyl enol ethers
ð80JCS"P0#340Ł react with phenyl sulfenyl chloride in the absence of organometallic reagents to give
a!sulfenyl aldehydes directly[ Despite the reactive nature of the electrophile\ dioxolanes\ ethers and
THP ethers have been shown to survive the sulfenylating conditions[ Hydrocinnamaldehyde reacts
directly with "methoxycarbonyl#sulfenyl chloride in the absence of a base to give a!"methoxy!
carbonylsulfenyl#hydrocinnamaldehyde "21# in 51) yield[ Under the reaction conditions\ elim!
ination does not appear to be a problem\ and the experimental procedure is very simple ð81JOC0942Ł[
CHO
Ph
S
CO2Me
(32)
O
OEt R1SNa then LDA, R2X
N R1S
Br N
OEt SAMP then O3
65–90% R1S OMe 45–80% R2
Scheme 37
The reaction of the formyl anion equivalent "22# with ketones results in an adduct which can
undergo rearrangement to an a!sulfenyl aldehyde on treatment with SOCl1 "Scheme 27# ð70TL776\
76RTC378Ł[ Although "22# will also add to aldehydes\ subsequent rearrangement does not proceed
smoothly unless SOCl1 is replaced by methanesulfonyl chloride ð77JA4198Ł[ This reaction is thought
to proceed via a 0\1!rearrangement of the phenylsulfenyl group\ and a similar mechanism must also
be involved in the bromination and hydrolysis of vinyl thioethers "Equation "29## ð63LA1974Ł[
Formylation of the anion derived from the boronate ester "23# with ethyl formate gives\ following
cleavage of the carbon0boron bond by hydrolysis\ a!sulfenyl aldehydes[ In a subsequent reaction\
a!sulfenyl aldehydes can undergo alkylation at the a position with reactive benzyl or allyl halides
ð71JOC1368Ł[ Stereocomplementary reduction of the oxazolidine "24# under chelation! or non!
chelation!controlled conditions can lead to either enantiomer of the corresponding hydroxy!
oxazolidine[ Thiolysis of each of these leads to enantiomerically pure a!"arylsulfenyl#propanal
ð82JOC2054Ł[
25 Alkyl Aldehydes
OH SPh
PhS OMe R1 R1
R1R2CO OMe SOCl2 O
R2 R2
Li
(33) SPh
Scheme 38
Ts
R1 O
N
B O
PhS O H O Ph
(34) (35)
The use of electrolytic methods for the interconversion of functional groups is attractive because
of the absence of expensive reagents and the reduced environmental hazards associated with the
disposal of by!products[ As part of the continuing search to exploit such procedures\ terminal
alkenyl sul_des ð70CC152\ 77CC0357Ł and alkenyl silanes ð82T1900Ł can be oxidized to a!phenylsulfenyl
aldehydes in the presence of thiophenol and O1[ For both substrates\ the same transformation can
be achieved without using electrolysis\ although the reaction is much slower[ For alkenylsilanes\
isolated alcohols and ketones can survive the reaction conditions[ Terminal alkenyl sulfoxides are
also intermediates to a!sulfenyl aldehydes[ The reaction involves treatment of a b!aryl or b\b!dialkyl
sulfoxide with NaOAc and Tf1O\ and proceeds via the acylals "Scheme 28# ð80TL5862Ł[ In a procedure
that has been widely adopted for the synthesis of a!heterosubstituted carbonyl compounds\ PhSNa
adds to a\b!epoxy sulfoxides\ for example "25#\ at the b position to give a!sulfenyl aldehydes after
elimination of phenylsulfenic acid ð74BCJ1738\ 81SL344Ł[ Amines\ THP ethers and alkyl chlorides are
some of the groups that remain una}ected[ The epoxy sulfoxides are easily prepared via a Darzens
reaction between the anion of a 0\0!chlorosulfoxide and a ketone[ Apparently\ fewer methods are
known for the synthesis of more remote sulfenyl!substituted aldehydes[ The addition of thiophenol
to acrolein has been reported\ but the product was only isolated after protection of the aldehyde
group with propane 0\2!dithiol ð68TL2056Ł[
Scheme 39
Li
O
O-THP O NR2
PhOS
O
(36) (37)
Silyl enol ethers derived from aldehydes react with chloroalkyl sul_des to give b!sulfenyl alde!
hydes ð68TL1068\ 77T3196Ł[ Many homenolate anions derived from aldehydes have been developed
ðB!76MI 290!91Ł\ and some of these\ for example "26#\ have been shown to react with electrophilic
sulfenylating agents at the g position to give protected b!sulfenyl aldehydes ð63JA4459\ 70AG"E#016Ł[
The silyl enol ether derived from isobutyraldehyde reacts with trimethylthio orthoformate in the
presence of SnCl3 to give 1\1!dimethyl!2\2!bis"methylthio#propanal ð74TL5402Ł "for reactions of
enolate donors with thionium ions to give g!sulfenyl ketones\ see Section 2[92[4[0#[
5!"Phenylsulfenyl#hexanal can be prepared in good yield by the photolytic cleavage of 1!"phenyl!
sulfenyl#cyclohexanol[ The application of this method to other ring sizes or more highly substituted
Bearin` a Selenium or Tellurium 26
systems would enhance its usefulness\ as the sulfenyl alcohols can be readily prepared from the
corresponding alkenes via the epoxides ð89TL52Ł[ The synthesis of a!sulphenyl aldehydes and ketones
has been part of a previous review ð66HOU"6:1C#1206Ł[
Ar O i, BF3•Et2O Ar
NR1R2 (31)
SO2Ar ii, R1R2NH ArO2S
H
OHC O OHC O
PhSeCl, 60 °C
O O (32)
AcO AcO
H
OAc OAc
O O SePh
PhSeNEt2, CH2Cl2
(33)
CHO 72% CHO
A number of aldehyde derivatives have been used as enolate donors during phenylselenylation
reactions[ For example\ enamines react directly with PhSeCl at −009>C ð79TL3306Ł or with selen!
amides to give mono! or bis!a!selenyl aldehydes ð71TL0446Ł\ and enol ethers react with PhSeBr
ð68HCA0395Ł or PhSeCl ð68S871Ł to give a!phenylselenyl aldehydes[ In the latter case there are some
interesting examples of chemoselectivity as\ at low temperatures\ silyl ethers\ isolated alkenes and
dioxolanes survive the reaction conditions "Equation "23##\ whereas at room temperature cyclic
acetals give selenylated products "Equation "24##[ Dihydropyran undergoes a regioselective addition
using PhSeCl in water to give a 1!hydroxy!2!"phenylselenyl#tetrahydropyran ð71TL1396Ł\ and silyl
enol ethers ð66S763Ł or silyl dienol ethers "Equation "25## ð67SC100Ł can be derivatized in the same
way[ Further examples of the selenylation of aldehydes can be found in the excellent review by Back
ðB!76MI 290!92Ł[
SePh
O PhSeCl, RT O
(35)
O 70% O
O
TMS-O PhSeCl
(36)
67%
SePh
Terminal alkenes can undergo oxyselenylation to give a!phenylselenyl aldehydes and:or a!phenyl!
selenyl ketones\ depending on the regiospeci_city of the addition[ As might be expected\ the latter
generally predominate\ although the ratio can be as low as 0 ] 0 ð70BCJ2099Ł[ The directing e}ect of
the oxygen atom in allylic ethers or silyl ethers results in regiochemically controlled addition to give
b!oxygenated a!phenylselenyl aldehydes "Equation "26## ð70BCJ2409Ł[ This directing e}ect of the
oxygen is strongly dependent on distance\ as the corresponding homoallylic ethers give no better
than a 2 ] 0 mixture of selenyl aldehyde to selenyl ketone ð70BCJ2409Ł[ The presence of a heteroatom
on the alkene can also control the regiochemistry of the addition "Equation "27## ð79CC840Ł[
TBDMS-O TBDMS-O O
Ph2Se2, (PhSeO)2O
(37)
Ph Ph
81%
SePh
TBDMS = t-butyldimethylsilyl
Se
OHC CHO
Ph Ph
(38)
Scheme 41
O O
Ph N N
NHZ NHZ N
N
(39) (40)
O O O OMe
i, Et3SiH, Pd on C
(39)
MeO SEt ii, CSA, MeOH MeO OMe
95%, 100% ee
t-BOCHN t-BOCHN
t-BOC = t-butoxycarbonyl
LSA = camphorsulfonic acid
In cases where the chemoselectivity for the reduction is low\ that is\ appreciable alcohol formation
results\ it may be more favourable to use excess reducing agent and then oxidize the resulting alcohol
back to the aldehyde[ Many reagents have been reported for the reduction\ including LiAlH3 ð80SC0Ł\
borohydrides ð82JOC2457Ł and sodium metal ð83TL0666Ł^ whilst for the subsequent oxidation the
ParikhÐDoering conditions "DMSO\ SO2 = py# often result in the least racemization\ although many
other useful procedures are known ð76AG"E#0030\ 89OPP288\ 83JA0205Ł[ 0\1! or 0\2!Amino alcohols
prepared using other methods can be oxidized in the same way to a! or b!amino aldehydes ð81T3120Ł[
Dipeptides containing serine can be prepared by the oxidative cleavage of a glucosamine amide
in which the sugar acts as the source of the serine residue "Scheme 31# ð81AG"E#0280Ł[ As might be
expected from this\ the oxidative cleavage of alkenes ð73TL0960Ł or 0\1!diols ð68CC764\ 75JOC4183\
78TL5658Ł having proximal amino groups has been used to prepare amino aldehydes[
The methods described above are ideal for the synthesis of N!protected a!amino aldehydes but
are less suitable if the requirement is for carbonyl!protected derivatives[ These can be made in a
complementary approach involving adjustment of the oxidation state at the amino terminus\ and
this is an ideal method for making low!molecular!weight building blocks in racemic or homochiral
form[ In one early example\ it was demonstrated that diethoxy acetonitrile was susceptible to
successive nucleophilic attack by organometallics to give a!disubstituted amino acetals "Scheme 32#
ð79S778Ł[ Glyoxal is an ideal starting material for a!amino aldehyde synthesis due to its low cost\
but methods for the selective functionalization of one of the aldehyde groups have not been widely
available[ However\ it has been demonstrated that the monoacetal of glyoxal can be prepared using
a number of di}erent alcohols in a very simple but high!yielding procedure[ The remaining aldehyde
group was subjected to a reductive amination\ using primary amines or ammonia\ also in high yield
"Scheme 33# ð77BSF84Ł[ As a logical extension of this work\ a number of groups have investigated
the use of chiral auxiliaries as a way of generating optically active amino aldehydes[ Chastrette and
Bearin` a Nitro`en 30
OH OH R
O H
NH3Cl i, ii
N iii, iv
O ZHN O NHZ
+ OH
HO 60–72% HO O 80–90%
OH R OH
OH OH
R O
H
N
ZHN
O
OH
i, NaOMe, DMF; ii, dicyclohexylcarbodiimide, hydroxybenzotriazole; iii, NaBH4, EtOH; iv, NaIO4, H2O
Scheme 42
co!workers have prepared a number of hydrazino acetals using di}erent diols "Scheme 34# and
determined that the acetals "30# and "31# give the best results\ with the addition of BunLi or MeLi
to "30# or "31# giving at least 73) diastereomeric excess[ Reduction of the hydrazine group then
gives the free amino acetal[ The enantiomer of the diol leading to "30# is available\ and so both
enantiomers of the amino acetal might be prepared using this approach ð89TL0318\ 81BSF050Ł[
Coordination of the nucleophile to the chiral auxiliary accounts for the transfer of chirality and this
can also be achieved using a chiral hydrazine[
Scheme 43
Scheme 44
Ph
Scheme 45
(41) (42)
The addition of Grignard or organolithium reagents to "32# in the presence of CeCl2 gives in most
cases at least 69) diastereomeric excess[ The N!protected amino aldehyde can be unmasked as
shown in Scheme 35\ with some observable loss of stereochemical integrity during the _nal step
ð82SL248Ł[ Using "S#!0!phenylethylamine as the chiral auxiliary\ the acetal of alanine can be prepared
in high chemical and stereochemical yield "Scheme 36#\ although the method works less well for
other amino aldehydes ð78S597Ł[ Alexakis and co!workers have used a C!1 symmetrical diamine as
31 Alkyl Aldehydes
the chiral auxiliary and achieved excellent yields of stereocomplementary products[ The addition of
organolithium reagents to the aminal "33# gives\ generally as a single diastereoisomer\ the adduct
"34# "Scheme 37#\ arising from the approach of the nucleophile from the bottom face of the
hydrazone ð80TL0060Ł[ Under identical reaction conditions Grignard reagents do not react^ however\
in a less polar solvent\ nucleophilic attack occurs from the opposite face with good selectivity
ð81JOC3452Ł[ The amino aldehydes can be unmasked under mild conditions and the chiral diamine
recovered\ if required[ Katritzky and co!workers have extended their elegant work using the chem!
istry of benzotriazole to the synthesis of amino aldehydes in excellent yields ð89S0062\ 80T1572Ł[
Primary and secondary amines can be introduced in this manner\ and variation of the group at the
a position is possible using the appropriate organometallic reagent "Scheme 38#[
OMe OMe CO2Bui
OMe N N
SAMP MeO N i, BuiMgCl, CeCl3 MeO N i, Li, NH3
Bui O
Scheme 46
OMe
OMe
(S)-1-(phenyl)ethylamine H2, 5 bar, Ni on Al
OMe
OMe
p-TsOH 92%, 90% de
Ph N
O
OMe
OMe
HCO2NH4, Pd on C
OMe
Ph NH 96%, 92% ee OMe
NH2
Scheme 47
Ph Me Ph Me Ph Me
N Bun BunMgBr, PhMe, THF N BunLi, Et2O N Bun
Scheme 48
N OHCCH(OEt)2 N i, R3MgX R3
N N
N R1R2NH N ii, HCl R1R2N CHO
H 70–80% OEt 60–90%
R1R2N
OEt
Scheme 49
Several research groups have used the thiazole moiety as an equivalent of the formyl anion and
demonstrated its ability to attack carbonyl compounds to give a!hydroxy aldehydes "see Section
Bearin` a Nitro`en 32
2[90[3[0#[ Dondoni and co!workers have studied its reaction with C1N systems and found an
excellent spectrum of reactivity with nitrones[ With nitrones derived from alkoxy aldehydes\ anti
addition is preferred and the initial products can be further elaborated to the desired systems
"Scheme 49# ð81TL3110Ł[ 0\2!Dithiane reacts with disubstituted imines to give amino aldehydes
ð63BSF220Ł or with nitriles to give the enamine "35#\ and reduction of this compound with diborane
gives the protected amino aldehyde "36# ð76CC664Ł[ Relatively few other formyl anion equivalents
are reactive enough to add to simple imines\ although those that do are included in an earlier review
ðB!76MI 290!90Ł[
O O– 2-lithiothiazole O N 3 steps O
O O O
N+ Ph 62%, 93% de S CHO
N Ph NHBOC
HO
Scheme 50
S NH2 S NH2
S Ph S Ph
(46) (47)
A number of papers have demonstrated the 0\1!migration of an amino group as part of a synthesis
of a!amino aldehydes[ The anodic oxidation of n!tosylamines generates the corresponding imine\
which rearranges to the enamine[ This enamine is su.ciently electron!rich to react with a positive
bromine species\ generated in situ\ and following aziridine formation the desired product is isolated
in reasonable yield "Scheme 40#[ The conversion is independent of steric factors\ as isolated yields are
similar for a!unsubstituted\ monosubstituted or disubstituted amino aldehydes ð75TL5972\ 89JA1257Ł[
Similar products are obtained from the treatment of enol ethers with N!halo amides ð67CJC008Ł[
N\N!Dialkyl enamines demonstrate a preference for the migration of the more electron!rich amino
group "Scheme 41# ð68AG"E#822Ł[
R1 R1 R1
–2 e– Br+/MeOH R2
NHTs NHTs NHTs
R2 R2 Br
OMe
R1 Ts R1
N R2
OMe
R2 50–60% TsHN
OMe OMe
Scheme 51
+ O
p-TsNHCl NHTs NR1R2 H3O+
NR1R2 Cl
NR1R2 R1R2N
NHTs
Scheme 52
The outcome of the reaction between ammonia or amines and a!halo aldehydes is strongly
dependent on the speci_c reagents\ but frequently fails to give the desired a!amino aldehydes[
Displacement with ammonia cannot be controlled in such a way as to prevent dimerization or
pyrazine formation\ whilst for primary amines the ambident reactivity\ carbonyl addition versus
halide displacement\ of the halo aldehyde tends to result in mixtures of products[ Using secondary
amines the initial products\ "37#\ can give rise to isomeric amino ketones "38# via an intramolecular
33 Alkyl Aldehydes
rearrangement "Scheme 42#\ although by careful control of the reaction conditions either product
can be obtained selectively[ Some of the problems associated with this transformation can be over!
come by protection of the aldehyde group as the acetal or imine prior to aminolysis ðB!77MI 290!90\
89JOC301Ł[
O O O
R2R3NH
R1 R1 NR2R3
R1
X NR2R3
(48) (49)
Scheme 53
O SOPh piperidine
N (40)
78%
CHO
N N OH
MgBr NaBH4
O 78%
86%
N LDA
Ph3PCHCO2Me methyl crotonate
85% 67%
OH
CO2Me CO2Me
N N
Scheme 54
O HN OMe
Scheme 55
Me
(EtO)2PO N
(50)
a useful method for the preparation of 0\2!bisheterosubstituted alkanes[ For example\ the reaction
of alkenes with nitrile oxides or nitrones leads to cyclic products which contain a masked b!amino
alcohol "Scheme 45#[ This can be released by reduction and:or ring cleavage "for reviews on 0\2!
dipolar cycloaddition reactions\ see ð80COS"3#0958Ł and ð80COS"3#0000Ł#[ In order to form the desired
amino aldehyde an additional oxidation step is required\ but this can be avoided by the use of an
enol ether rather than an alkene "Scheme 46# ð73JA4487Ł[
R4 R4
N R1 R5 N+ N
R3 R3 N O– O– R5
O O
R2
R1 R2 R1 R2
Scheme 56
The Mannich reaction to prepare b!amino carbonyl compounds is one of the best known reactions
for the preparation of amino ketones "see Section 2[92[6[0"ii##\ but it has rarely been applied to the
synthesis of amino aldehydes\ perhaps because under classical Mannich reaction conditions the
aldehyde undergoes rapid self!condensation[ The dimethylaminomethyl group can\ however\ be
introduced using an in situ!formed iminium salt and a silyl enol ether in DMSO "Equation "30##
ð79CL0102\ 71BCJ423Ł or an iminium salt and an enolate anion at lower temperature in THF ð66JA833Ł[
35 Alkyl Aldehydes
O O OMe
O O HCl, MeOH, H2, Pd(OH)2
OEt
O
93%
H H
+ O– 74%
N N NH2
Ph
O OH
Ph
OEt
Scheme 57
O-TMS NMe2
CHO
Me2NCH2NMe2
(41)
ClCH2I
71%
OEt
NO2
EtO
(51)
NMe2
N
NMe2 OAc OAc OAc OAc
i, O3
N H + AcO NO2 AcO NO2
91% ii, Me2S
H OAc OAc OAc OAc 85%
enantiomeric selectivity 3.6 : 1
OAc OAc
Scheme 58
NO2 O OMe
i, O3, Me2S TBDPS-O
(44)
TBDPS-O
ii, MeOH, H+
76%
O2N
OH
O CHO
OH O
O2N NaIO4
CHO (45)
92% O2N
BnO OH
OBn
CHO
CHO NO2
N i, LDA, –78 °C to 0 °C NO2
+ (46)
O ii, reduction
55%
Among the more unusual nitrogen!substituted aldehydes that have been prepared\ a\a!
disubstituted aldehydes react\ via their silyl enol ethers\ with NOCl to give a!nitroso aldehydes[ The
products are stable at 9>C but dimerize at higher temperatures and decompose on silica gel
ð63JOC1447Ł[
Diazoacetaldehyde dimethyl acetal can be prepared from the corresponding amino compound
ð56CB0380Ł[ A more general procedure\ and one which gives the free diazo aldehyde\ involves the
reaction between a b!amino a!substituted enal and p!TsN2\ which may proceed via the intermediate
37 Alkyl Aldehydes
triazoline "Scheme 48# ð69CCC2507\ 60OPP116Ł[ The chemistry of diazo compounds has been the
subject of a monograph ðB!75MI 290!91Ł[
R2R3N R1
CHO p-TsN3 CHO R1 CHO
R2R3N
R1 N N N2
Ts N
Scheme 59
The addition of nucleophiles to a\b!epoxy sulfoxides to generate a!amino aldehydes has already
been mentioned "see Equation "39##\ and a similar approach using NaN2 and a\b!epoxy sulfones
has been used to introduce an azide group at the a position ð67JOC1955Ł[ Oxidative cleavage of
alkenes and 0\1!diols are well!known routes to aldehydes\ and the azide group has been shown to
survive both transformations ð80JOC2738\ 82TL392Ł[ Azide is\ in fact\ a relatively powerful nucleophile
which attacks enals at the b position to give b!azido aldehydes or b!azido acetals "Equation "36##
ð40JA4137\ 78JA2813\ 80JOC2480Ł[
O OH
CHO NaN3, AcOH
BzO
(47)
BzO
OH 95%
N3
(54) (53)
Scheme 60
The preparation of simple arsonium salts is the same as for phosphonium salts involving dis!
placement of a halide by an arsine[ Thus\ triphenylarsonium acetaldehyde "44# has been prepared
in 89) yield from the reaction between triphenylarsine and bromoacetaldehyde ð74TL5336\ 77TL2838Ł\
and the arsines "45# and "46# are also known ð75TL3472\ 78TL068Ł[ Arsonium ylides stabilized by two
Bearin` a P\ As\ Sb or Si 38
carbonyl groups\ "i[e[\ "47## can be prepared directly from the condensation of an arsine oxide with
a 0\2!dicarbonyl compound[ Reviews on arsonium ylides have been published ð76CSR34\ B!89MI 290!
91Ł[
O O
+ + +
Ph3As CHO Ar3As CHO Ar3As OPri –
R R
+
OPri AsPh3
(55) (56) (57) (58)
Scheme 61
O
P
PriO NMe2
i
Pr O
(59)
O
i, LDA, –78 °C
P (48)
NBut EtO NHBut
ii, (EtO)2POCl EtO
O O O
cyclohexylamine i, EtMgBr
P CHO P c-C6H11 P c-C6H11
EtO EtO N EtO N
75% ii, MeI
EtO EtO EtO
H 40% H
Scheme 62
O
P CHO
HO
HO
(60)
49 Alkyl Aldehydes
The attack of phosphorus"III# nucleophiles at imines or halides has been used to prepare formyl!
substituted phosphonates[ Addition to the former "Equation "38## has been demonstrated to give
high yields of adducts\ and to occur chemoselectively in the presence of aldehydes and ketones
ð89T6064Ł[ In the latter\ the substitution occurs with bromoacetaldehyde diethyl acetal and also with
2!bromopropionaldehyde diethyl acetal\ where substitution at the a or b positions of the acetal is
tolerated[ Additional substituents can then be introduced by alkylation adjacent to the phosphonate
group "Equation "49## ð70T0266Ł or by a Mannich reaction to give intermediates to a range of
heterocycles "Equation "40## ð74T316Ł[ The Arbuzov reaction of trialkyl phosphites with a!halo
aldehydes cannot be used as a method for the preparation of formyl phosphonates due to the
predominance of two competing reactions "Scheme 52# ðB!77MI 290!90Ł[
PO(Ph)OBu
BuO(Ph)PO-TMS
EtO Bn EtO Bn (49)
N N
81%
OEt OEt H
O O
i, BunLi
P OEt P OEt (50)
EtO EtO
EtO ii, EtI EtO
OEt 70% Et OEt
O O
P CHO DMF, heat P CHO
EtO EtO (51)
EtO EtO
NMe2
O-TMS
P(O-TMS)3 R1 CHO P(OR2)3
R1 R1
PO(O-TMS)2 OPO(OR2)2
X
X
Scheme 63
In a reaction related to that shown in Scheme 50\ the b!keto esters "50# undergo a further
formylation via their a\g!dianions to give "51# ð81SC108Ł[ Aldehyde enolates react from the a position
with diethyl chlorophosphite\ and exposure of the adducts to air gives the phosphonates "Scheme 53#
ð80JOC4445Ł[
O O O O
P R2 P CHO
EtO EtO
EtO EtO
R1 R1 R2
(61) (62)
O OK O
KH i, ClP(OEt)2
ii, air
41% PO(OEt)2
Scheme 64
Treatment of the vinylphosphonium salts "52# with ethoxide had been postulated to give the
ylides "53#\ but a re!examination of the evidence has lead to the reassignment of the products as the
phosphine oxides "54# "Scheme 54# ð81TL750Ł whilst similar products can be made from the addition
of phosphorus halides to ethyl vinyl ether ð76JGU192Ł[ The presence of a chlorine on the epoxide
"55# directs nucleophilic attack by trialkyl phosphites to the b position[ A carbonyl group is formed
by a 0\0!elimination of chloride\ which then proceeds to promote an Arbuzov reaction to give "56#
ð71CB590Ł[
Bearin` a Metalloid 40
R1 +PPh
3 P(O)Ph2
OEt NaOEt NaOEt
Ph3P R1 R1
OEt OEt OEt
(64) (63) (65)
Scheme 65
O Cl R1 CHO
R1 PO(OEt)2
(66) (67)
Among the methods that have been developed to deliver a phosphorus nucleophile to the b
position of an enone "see Section 2[92[7[1"ii##\ very few have been reported as being e}ective for
enals\ and those that are tend to give 0\1 adducts also[ One approach that does work involves simple
mixing of diethyl methyl phosphinate with an enal to give "57# ð77JOC3958Ł[
O
EtO P
Me
EtO OEt
R2 R1
(68)
HO OH TBDMS
TFA
(52)
86%
n-C6H13
TBDMS n-C6H13
O
O O3 O
N i, LDA N
SAMP Ph
OMe N OMe
N 42% overall, >96% ee
ii, TBDMS-OTf TBDMS
Ph TBDMS
Ph Ph
Scheme 66
92 : 8
Copyright # 1995, Elsevier Ltd. All R ights Reserved Comprehensive Organic Functional Group Transformations
3.02
Aldehydes: a,b-Unsaturated
Aldehydes
WARREN J. EBENEZER and PAUL WIGHT
ZENECA Specialties, Manchester, UK
2[91[0 ALDEHYDES BEARING AN a\b!ALKENIC BOND 43
2[91[0[0 a\b!Unsaturated Aldehydes Without Further Unsaturation 43
2[91[0[0[0 By elimination reactions 43
2[91[0[0[1 By oxidations of alcohols and their equivalents 46
2[91[0[0[2 Oxidation of allylic methyl `roups 47
2[91[0[0[3 By formylations of alkenes 47
2[91[0[0[4 By rearran`ements of a!acetylenic alcohols 48
2[91[0[0[5 By displacements of b!leavin` `roups 48
2[91[0[0[6 By aldol condensation reactions 48
2[91[0[0[7 By Witti` reactions 59
2[91[0[0[8 By DielsÐAlder reactions 50
2[91[0[0[09 By isomerisations 50
2[91[0[0[00 By reductions 50
2[91[0[0[01 From epoxides 51
2[91[0[0[02 Miscellaneous methods 51
2[91[0[1 a\b!Unsaturated Aldehydes With Further Unsaturation 51
2[91[0[1[0 By elimination reactions 51
2[91[0[1[1 By formylations of dienes 53
2[91[0[1[2 By oxidations of alcohols and reductions of acids 53
2[91[0[1[3 By rin` openin` reactions of pyrilium salts and furans 53
2[91[0[1[4 By Witti` reactions 54
2[91[0[1[5 From cyclopropanes 54
2[91[0[1[6 Miscellaneous reactions 55
2[91[0[2 Halo`enated a\b!Unsaturated Aldehydes 55
2[91[0[2[0 1!Halo`enated a\b!unsaturated aldehydes 55
2[91[0[2[1 2!Halo`enated a\b!unsaturated aldehydes 57
2[91[0[3 Oxy`en Substituted a\b!Unsaturated Aldehydes 60
2[91[0[3[0 1!Oxy`en substitution 60
2[91[0[3[1 2!Oxy`en substitution 60
2[91[0[4 a\b!Alkenic Aldehydes with Sulfur Substituents 61
2[91[0[4[0 1!Thio a\b!unsaturated aldehydes 61
2[91[0[4[1 2!Thio a\b!unsaturated aldehydes 61
2[91[0[5 Selenium Substituted a\b!Unsaturated Aldehydes 63
2[91[0[6 Nitro`en!Substituted a\b!Unsaturated Aldehydes 63
2[91[0[6[0 a!Nitro`en substituted a\b!unsaturated aldehydes 63
2[91[0[6[1 b!Nitro`en substituted a\b!unsaturated aldehydes 64
2[91[0[7 a\b!Alkenic Aldehydes with P\ As\ Sb\ or Bi!based Substituents 66
2[91[0[8 a\b!Alkenic Aldehydes with Si!based Substituents 66
2[91[0[09 a\b!Alkenic Aldehydes with Metal Substituents 67
2[91[1 ALDEHYDES BEARING AN a\b!TRIPLE BOND 67
42
43 a\b!Unsaturated Aldehydes
2[91[0 ALDEHYDES BEARING AN a\b!ALKENIC BOND
PdCl2(PhCN)2
N-methyl morpholine
O AgOTf, THF O
O O (1)
62%
O O
i, Br2, CaCO3, CHCl3
ii, PhNEt2, 100 °C
(2)
77%
i, NBS, CCl4 O
ii, NaOH, MeOH
OAc (3)
n-C5H11 n-C4H9
86%
i, THF, -95 °C
Cl ii, LiClO4, CaCO3, 130 °C
+ Li O (4)
O Cl 74%
SMe
Li+ HgCl2, MeOH, H2O O
n-C5H11Br + – n-C5H11
MeS SMe 84% n-C5H11
SMe
(a)
Scheme 1
HgCl2
HO (5)
66%
SPh O
i, PhSH
ii, H+ O
HO (6)
60%
SPh
i, HCl, H2O, MeCN
ii, HgCl2, HCl O
Ph (7)
98% Ph
OMe
O O
OH H3PO4
(8)
89%
H H
OH OH
OAc
dbu EtO
EtO O (9)
O
77% EtO
EtO
dbu = 1,5-diazabicyclo[5.4.0]undec-5-ene
45 a\b!Unsaturated Aldehydes
OEt
HCO2H, HCO2Na, H2O, 100 °C
EtO O (10)
82%
EtO
i, TMS-Cl, Et3N Ph
O OH ii, PhCH2MgCl O
iii, p-TsA, pyr
(11)
65%
i, LDA, HMPA
O ii, (CO2H)2
+ Et2N CN n-C5H11 O (12)
n-C5H11 50%
LDA = lithium diisopropylamide
HMPA = hexamethylphosphoramide
TMS TMS O
i, PhSCl, Et3N
OH LiAlH4 OH ii, AgNO3, H2O
68%
Scheme 2
O O O O
H i, PhSeCl, pyr
ii, H2O2
(13)
100%
H H
i, LDA, THF
ii, ketone
iii, H2O2
+ OH (14)
PhSe SePh
77% O
O
i, O3, –78 °C
O SPh ii, Me2S
O
iii, CCl4, 70 °C
O (16)
66%
OH i, (COCl)2, DMSO O
ii, Et3N
iii, Ac2O, pyr
(17)
O 70%
AcO AcO OAc
H
O OH
OEt O
+ – + (18)
Ph3As OEt 58%
MnO2, hexane, 0 °C
(19)
OH 97%
O
47 a\b!Unsaturated Aldehydes
OH pcc, 25 °C
(20)
90% O
pcc = pyridinium chlorochromate
i, 3M NaOH
ii, H2SO4
NO2 O (21)
68%
i, LDA, THF
ii, Me2S2
S iii, HgCl2, H2O
n-C5H11 O (22)
n-C5H11 S NMe2 78%
SeO2, EtOH, 50 °C
MeO2C MeO2C O (24)
48%
HCl, 0 °C O
MgBr + Me (26)
Ph N N 70% Ph
CHO
Pri Pri
i, BusLi
O2S ii, DMF
O (27)
N Pri 56%
N H
i, Pd(PPh3)4
O ii, Bu3SnH, toluene O
+ CO (28)
I 83% CHO
a\b!Alkenic Bond 48
2[91[0[0[4 By rearrangements of a!acetylenic alcohols
Although a!acetylenic alcohols would normally rearrange to a\b!unsaturated ketones with acid
catalysts "see Section 2[94[0[0[6#\ alternative conditions have been found that give a\b!unsaturated
aldehydes[ This is e}ectively the anti!Markovnikov hydration of the alkyne[ The commonest reagent
is "Ph2SiO#VO and the reaction is proposed to go through a vanadate ester\ as in Scheme 2 ð65S14Ł[
For other examples see ð74TL4474\ 89TL6410Ł[
OSiPh3
OH Ph3SiO V
O
O
O
H (Ph3SiO)3VO, 146 °C
O
91% H
H H
O H H
O
O
H
H H
O
Scheme 3
i, BuLi S
EtO O + (29)
S S O
ii, H+ S
CHO CHO
H H
59 a\b!Unsaturated Aldehydes
CHO
TiCl4, PhNH2Me•O2CCF3
(31)
50% O
O O CHO
Intermolecular aldol condensations are equally facile occurring under a range of conditions
"Equation "21## ð40HCA0371\ 57JOC664\ 64JCS"P0#0416\ 66JOC1012Ł[ The control of the regio chemistry
for unsymmetrical condensations can be achieved by the use of enol ethers and enamines ð66JA6254\
76JOC3677\ 77TL3606Ł or a!lithioimines and a!lithiohydrazones ð58JOC0011\ 65TL6\ 67JOC2677Ł[ The
Mannich reaction\ followed by elimination of the b!amino group from the intermediate Mannich
base\ is closely related to the aldol condensation and is often used to prepare a!methylene!aldehydes
ð32CB0379\ 72TL0060\ 78CL0172Ł[
C5H11
H2BO2, m-xylene, 138 °C
C6H13CHO C6H13 (32)
100% CHO
i, NaH CHO
O H O ii, H3O+
N 25 °C
(OEt)2P + (34)
86%
(1)
+ Ph CHO O
Ph3P OMe Ph (35)
(2)
TBDMS = t-butyldimethylsilyl
a\b!Alkenic Bond 50
2[91[0[0[8 By DielsÐAlder reactions
The DielsÐAlder reaction enables the synthesis of cyclic a\b!unsaturated aldehydes via the use of
formyl substituted diene systems ð71TL1700\ 78CB474Ł or alkynic aldehydes "Equation "26## ð70TL514\
72AG"E#309\ 76JOC3024Ł[
OAc OAc
70 °C
CHO + (37)
89%
OHC
OAc OAc
2[91[0[0[09 By isomerisations
The isomerisation of bg!unsaturated aldehydes also furnishes a\b!unsaturated aldehydes and can
occur under acidic ð68S021\ 76JCR"S#185Ł or basic conditions ð79HCA0554Ł[ The isomerisation of
propargylic ethers to allenic ethers followed by hydrolysis similarly furnishes a\b!unsaturated alde!
hydes "Equation "27## ð54RTC20\ 61TL0704Ł[ g!Hydroxy!a\b!unsaturated aldehydes can be prepared
by the deprotection and hydroxy!rearrangement of tertiary carbinols such as "2# "Equation "28##
ð67TL0294\ 76SC044Ł[
CHO
i, NaNH2, NH3, –33 °C
OEt ii, 5N H2SO4, 70 °C
(38)
70%
S CHO
HgO, HBF4
HO S H2O, THF, reflux
(39)
84%
OH
(3)
2[91[0[0[00 By reductions
a\b!Unsaturated aldehydes can be prepared by the diisobutylaluminum hydride "dibal!H#
reduction of a\b!unsaturated nitriles ð70JOC3706\ 70TL0068Ł or the reduction of a\b!unsaturated
acid chlorides using poor hydride donor reducing agents such as NaBH"OMe#2 "Equation "39##
ð47CB1341Ł[ In a similar fashion oxazines have been used as protected carboxylic acid equivalents
and can be reduced and hydrolysed to the aldehyde using sodium borohydride "Equation "30##
ð62JOC25\ 63JOC512Ł[ Benzoisothiazoles have been used in an analogous fashion in the synthesis of
a\b!unsaturated aldehydes\ acting as a formyl anion equivalent ð67TL4Ł[
OAc OAc
AcO NaBH(OMe)3 AcO
(40)
OHC
CHO i, BunLi, –78 °C
ii, NaBH4, EtOH, –40 °C
iii, H3O+
O + (41)
53 °C
N
51 a\b!Unsaturated Aldehydes
2[91[0[0[01 From epoxides
Epoxides are useful intermediates in the synthesis of a\b!unsaturated aldehydes[ Thus the
DarzensÐClaisen reaction was used by Isler et al[ in the _rst synthesis of vitamin A "Scheme 3#
ð36HCA0800Ł "also see ð47JOC046Ł#[ Related reactions involve the acid catalysed rearrangement of
a!epoxy sulfoxides\ ð66TL0266\ 78JA6493Ł\ a!epoxy nitriles ð52JIC003Ł and a!epoxy silanes ð71CL0886Ł
yielding a\b!unsaturated aldehydes[ The pinacol type rearrangement of an a!hydroxy epoxide
similarly leads to an unsaturated aldehyde ð62JOC0279Ł as does the oxidation of a terminal epoxide
using sulfuryl chloride ð76TL1064Ł "Equation "31##[
O
O
NaOEt, –10 °C CO2Et 15% NaOH, MeOH, 5 °C
+ Cl CO2Et
80% overall
steps
CHO Vitamin A
Scheme 4
O O O O
H H H H
SO2Cl2, CH2Cl2, 39 °C
(42)
90% CHO
O
H CO2Me H CO2Me
i, Li
O ii, H2SO4
(44)
Ph
Ph SBut 98%
EtO O
OH
i, H2/Pd-BaSO4
ii, HCl
(45)
85%
O i, BuLi O
O OEt ii, MsCl, Et3N O
+ Bu3Sn (46)
iii, NaHCO3
H H H H
d!Hydroxy groups can be eliminated from a\b!unsaturated aldehyde as part of a similar procedure
that a}ords a 3!carbon homologation "Equation "36## ð89SC1872Ł[ "1"E#\3"E##!Isomers are exclus!
ively formed from aldehydes in this reaction\ whereas use of unsymmetrical ketones gives mixtures
of "1"E#\3"E## and "1"E#\3"Z##!isomers[ The 3!lithioalkoxydiene can also be made by hydro!
stannylation of an alkoxyenyne\ followed by tin:lithium exchange ð67TL606Ł[ Alternatively\ the
alkoxyenyne can be used directly "Equation "37##\ with the alkyne then being partly reduced with
LiAlH3\ followed by acid!catalysed hydrolysis and elimination ð45JCS3971Ł[ See ð47JOC0479Ł for a
similar example\ and also note ð76HCA0399Ł for an example of d!OH elimination using basic
conditions "NaHCO2:THF#[ d!Methoxy groups are often eliminated under basic conditions\ for
example\ dbu ð64CL0190\ 66BCJ0050Ł\ or NaOMe ð61CC752Ł[
TMS-O i, ButLi
ii, Aldehyde
O iii, HCl
+ Ph O (47)
Ph 72%
Br
O Li
i, aldehyde
ii, LiAlH4
iii, H2SO4
+ (48)
52%
OMe OMe
OMe
Ph
S O
O O toluene/reflux
(49)
85%
53 a\b!Unsaturated Aldehydes
2[91[0[1[1 By formylations of dienes
Direct Vilsmeier formylation of dienes and trienes is possible\ especially if they are electronically
activated or electron rich\ "Equation "49## ð66TL1018Ł[ Cycloheptatriene reacts similarly ð67CL30Ł\
as do dihydropyridines "Equation "40## ð89JOC181Ł^ see ð55CB1368\ 55CB2946Ł for other examples[
The b!methyl enone in Equation "41# is formylated under similar conditions to give a good yield of
a chlorodienal ð65RTC297Ł[ Lithio dienes can also be used as the nucleophile ð65ZN"B#0543Ł[ A
vinylogous formylation a}ording a 2!carbon homologation can be achieved using b!dimethyl!
aminopropenal ð89TL0254Ł or triformylmethane ð61CB0704Ł[ Takahashi and co!workers have inves!
tigated the use of a Rh3"CO#01 catalyst to hydroformylate enynes\ producing dienals ð75TL3386\
77BCJ3242Ł[
Me POCl3, 25 °C
+
+ N (50)
Me Cl 80%
O
SiPri3
SiPri3
DMF, POCl3, CH2Cl2
(51)
Ph N 97%
Ph N
CO2Ph
CO2Ph
O Cl
DMF, POCl3, 80 °C
(52)
80%
O
Ried has investigated reduction of dienoic acids\ via the acid chlorides\ which are reacted with
2\4!dimethylpyrazole\ and subsequently reduced with LiAlH3 "Equation "43## ð48LA"511#26Ł*this
also works for vitamin A acid[
i, 3,5-dimethylpyrazole
O ii, LiAlH4 O
(54)
Cl 74%
Li THF, –78 °C
+ (55)
+
O 69%
i, LDA, THF
ii, NH4Cl
NHCOPh O NHCOPh (56)
O 95%
O i, ButOK, THF
ii, H3O+
O O + OHC (58)
78% OHC
P(OEt)2
CHO
N2
S
Rh2(OAc)4, 0 °C S
N + (59)
O O 100% N
CO2CHPh2 O
CO2CHPh2
55 a\b!Unsaturated Aldehydes
N2
O
O Rh2(OAc)4, CH2Cl2, 20 °C
(60)
95%
O CHO
CHO
CHO PhCHO, 37% HCl, 20 °C
(62)
88%
Ph
(5)
O2N NO2
+ H
N N
HO–
NO2 (63)
73%
NO2 OHC
(6)
CO2Et EtO2C
O EtOH, 78 °C
+ (65)
90% O
H 2N NH2
Scheme 5
A second general method for the preparation of 1!~uoro!1!alkenals involves the reduction and
subsequent rearrangement of 0\0\1!tri~uoro!2!hydroxy alkenes[ Thus 0\0\1!tri~uoro!2!hydroxy!0!
alkenes "6# are prepared in good yield by the addition of tri~uorovinyllithium to carbonyl
compounds[ Nucleophilic replacement of one ~uorine atom by hydride is achieved using lithium
aluminum hydride in ether and the resulting di~uorovinyl alcohols "7# undergo rearrangement in
85) sulfuric acid at low temperature to give the ~uoro aldehyde product "8# generally as a mixture
of stereoisomers "Scheme 5# ð67S017Ł[ The use of 0!chloro!1\1!di~uorovinyl lithium in place of
tri~uorovinyl lithium in an analogous reaction yields the corresponding 1!chloro!1!alkenals in very
good overall yield ð67S347Ł[
F F
F F R1
R1 LiAlH4, Et2O 98% H2SO4
F Li R1 F R1 CHO
O
THF, Et2O R2 76–82% R2 40–69%
R2
R2 MO F MO F F
(7) (8) (9)
Scheme 6
1!Iodo!1!alkenals "00# can be prepared under mild conditions in a one!pot procedure from
acetylenic alcohols "01# using a pdc oxidation of the derived iodine complex "Equation "56##[ Yields
are good and unsymmetrical aldehydes yield a single geometric isomer as the product ð70TL0930Ł[
i, I2, RT
R1 R1 CHO
ii, pdc, RT
R2 (67)
HO 30–66% R2 I
(12) (11)
O O
Cl2, H2O Cl
(69)
O O
SOBr2
(70)
85%
Br
The Wittig reaction has been used to prepare a!halo alkenals ð51CB2992Ł[ The formyl methylene!
phosphorane "02# is _rst halogenated with molecular halogen to give the haloformyl methylene
phosphorane "03#[ This reacts with aldehydes in the normal manner to give the desired 1!haloalkenals
"Scheme 6#[ Preparation of the "Z#!1!bromo!alkenal "04# can be achieved stereospeci_cally from the
readily available "E#!bromoacetal "05# by formolysis accompanied by concomitant "E# to "Z#!
isomerisation in 66) yield "Equation "60## ð66S531Ł[ 1!Chloro!1\3!pentadienal "06# was formed by
the thermolysis in quinoline of the pyran "07#\ which is easily prepared from 1\2!dihydrofuran
"Equation "61## ð53T1980Ł[
X2
X PhCHO X
O
Ph3P O Ph O
X = Br, Cl Ph3P X = Br, 34%
X = Cl, 52%
(13) (14)
Scheme 7
Cl Cl
quinoline, 120 °C
(72)
44%
O Cl O
(18) (17)
Me + Me Me + Me
N N
O
R1 O O
R2 +
R1 R1
R2 R2
Me + Me
N
O Cl
Cl–, H2O
R1 R1
R2 R2
Me + CHO
N
Me
Scheme 8
CHO
DMF, POCl3
(73)
O 83%
Cl
O N Cl Cl
CHO OHC
+ (74)
POCl3
OH
O Cl
POCl3, DMF
(75)
91%
CHO
POCl3 Cl
(76)
50%
N O N CHO
69 a\b!Unsaturated Aldehydes
O Cl Cl
POCl3, DMF OHC
+ (77)
CHO
( )n ( )n ( )n
(a) (b)
n (a) (b)
1 60 : 40
2 90 : 10
3 95 : 5
4 100 : 0
Cl
O
POCl3, DMF CHO
(78)
84%
O
i, ClCOCl
ii, H2O
Cl (80)
84%
NMe2 CHO
(20) (19)
O Cl Cl
SOCl2 H2O
57% overall
OMe Cl OMe O
(21)
Scheme 9
"ii# Miscellaneous
Dialkyl alkynes can be chloroformylated with dichloromethyl ether and boron trichloride
"alkenes\ however\ add twice to this reagent under these conditions# "Equation "70## ð77CB080Ł[
Again\ a mixture of "E# and "Z# stereoisomers results from this reaction[ No nonsymmetric alkynes
were considered in this paper so the regiochemistry of this reaction is unknown[ Treatment of the
trichloromethyl substituted cyclohexadienol "11# with 09) sulfuric acid at room temperature yields
the b\b!dichloroalkenal "12# in 89) yield\ "Equation "71## ð45JOC527Ł[
Cl Cl
OMe
Cl
(81)
BCl3
51%
O
a\b!Alkenic Bond 60
Cl3C
10% H2SO4
(82)
Cl
HO
Cl O
(22) (23)
OH
i, DMSO, (ClCO)2 O
Br O ii, Et3N
Br O (83)
79%
S
(24)
i, BunLi
ii, PhCHO
Br O
iii, HCl, H2O
(84)
MeO OMe 76% Ph OMe
O
i, DMF, POCl3
ii, 5% NaOH
(85)
O Ph 58%
O Ph
O
Cl3CCO2Et Cl Cl
ButO– H+
O EtO– O Cl O OBut
O
Scheme 10
61 a\b!Unsaturated Aldehydes
Bun O Bun O
+ (86)
EtO 63%
O EtO O
The addition of alcohols to propargylic esters\ followed by reduction to the allylic alcohols
and subsequent oxidation constitutes a useful and stereoselective synthesis of 2!alkoxy acroleins
"Equation "76## ð72TL4198Ł[ 2!Alkoxy substituted allylic alcohols have also been oxidised by other
reagents\ for example\ pcc ð66CC797\ 53CB0848Ł[ Other methods reported for the synthesis of 2!oxygen
substituted acroleins are] the reaction of the corresponding 2!halo "or ammonium# acroleins with
alcohols ð66JPR0931\ 89CB288Ł and Pd catalysed oxidation of a!silyl substituted allylic tosylates
ð74TL728Ł[
i, MeOH
ii, dibal-H
iii, MnO2 O
CO2Me (87)
70% MeO
Scheme 11
i, NaI, MeCN
SPh ii, TMS-Cl
SPh (88)
100%
MeO CHO
(28) (29)
Ph OH Ph
TFA, CHCl3
(89)
OMe 83%
PhSO2 OHC SO2Ph
(31) (30)
O O
i, Na2S
ii, PhCHBrCO2Et
Ph (91)
85%
Cl S CO2Et
(36) (35)
SH S O
H2O, NaOH
+ O NMe3+ ClO4– (93)
CO2Me 90%
CO2Me
(39)
The aldehyde "39# was prepared in 71) yield via a simple Wittig condensation with glyoxal
at room temperature\ using triethylamine to generate the requisite ylide in situ "Equation "83##
ð69JCS"C#1301Ł[
S i, TEA, THF S
S ii, glyoxal, H2O
S O
PPh3+ BF4– (94)
S 82% S
S S
(40)
The 0\1!dithiole "30# has been prepared by ring opening of the thiopyran "31# and subsequent
intramolecular oxidative coupling "Equation "84## ð58CC355\ 61T4086Ł[ Other routes to these
2!acylmethylene!2H!0\1!dithioles are also available ð47CB0113\ 52JA2133\ 55JOC2378\ 57JCS"C#1432\
61BSF3465Ł[
O
i, NaOH, H2O, DMF CHO
ii, K3Fe(CN)6
(95)
77% S
Ph S
Ph S
(42) (41)
A Vilsmeier formylation of an activated alkene or heterocycle has also been used to prepare
b!thioalkenals[ Thus the diene "32# was formylated at 9>C to yield the unsymmetrical aldehyde "33#
"Equation "85## ð78TL4178Ł\ and the 0\3!benzooxathiin "34# was formylated at room temperature to
give the corresponding aldehyde "35# "Equation "86## ð59JOC42Ł[ Formylation of the 0\3!benzodithiin
"36# provides the a\b!dithioalkenal "37# in moderate yield "Equation "87## ð42JA0536\ 43JA0957Ł[
Similarly formylation of tetrathiafulvalenyl lithium "38# with dimethylformamide produced the
corresponding aldehyde "49# "Equation "88## ð68JOC0365Ł[
63 a\b!Unsaturated Aldehydes
MeO2C S MeO2C S CHO
S CO2Me (COCl)2, DMF, 0 °C S CO2Me
S S (96)
MeO2C 75% MeO2C
S CO2Me S CO2Me
(43) (44)
S S
POCl3, DMF
(97)
27%
O O CHO
(45) (46)
S S
POCl3, PhNMeCHO
(98)
54%
S S CHO
(47) (48)
S S Li S S CHO
DMF, –70 °C to –20 °C, Et2O
(99)
44%
S S S S
(49) (50)
O
O PhSe N O
(100)
65%
SePh
i, BuLi
O
ii,
O
SeMe
n-C10H21 NHMe
n-C10H21 (101)
SeMe
SeMe
Scheme 12
O Cl
i, POCl3, DMF CHO
MeO ii, H2O MeO
(103)
N SO2Me 25% N SO2Me
MeO MeO
(56)
Me O
NHMe i, Hg(OAc)2, Et3N N
OH ii, NaBH4 Ph
+ (104)
54% Me
N
Ph
(57)
O
O OH H
O toluene, Na2SO4 O N
+ (105)
NH2 60%
CO2Me
CO2Me
(58) (59)
(E):(Z) 95:5
65 a\b!Unsaturated Aldehydes
NO2
NH2
O O H
O N
20 °C
+ (106)
40%
NO2
(60)
NaOMe, MeOH H
O MeO2C N (107)
CHO MeO2C NH3 + CHO
Ph Ph
(61) (62)
i, POCl3, DMF O
OMe ii, K2CO3
NMe2 (110)
71%
(65) (66)
A related method involves reacting the lithium salts of alkanoic acids with an aminomethyl!
eneating reagent\ preferably N\N!dimethylmethoxymethaneiminium methyl sulfate "56#\ to give the
amino compounds "57# via a decarboxylative double formylation "Equation "000## ð73JOC0177Ł[ "Z#!
b!Aminoacroleins have been prepared from b!lithioenamines\ which are themselves prepared by
metal halogen exchange[ Thus in Scheme 02\ the enamine "58# is _rst halogenated and then the
halogen is exchanged for lithium to give the stereochemically pure "Z#!b!lithioenamine[ This can
then be reacted with DMF to a}ord the enaminoaldehyde "69# ð72JCR"S#111Ł[
O
MeO
LDA (2 equiv.)
CO2H + Ph
Ph + (111)
N 35%
Me Me
NMe2
(67) (68)
Oxidative addition of amines to propargylic alcohols in the presence of activated MnO1 has been
reported\ and gives moderate to good yields of b!amino!acroleins "Equation "001## ð60ZOR1019Ł[
Alternatively\ alcohols can be added to 2!amino!propynals[ Thus 2!N\N!dimethylaminopropynal
a\b!Alkenic Bond 66
But But But
Br CHO
i, Br2 i, BunLi
N N N
ii, Et3N ii, DMF
O O O
(69) (70)
Scheme 13
"60# reacts smoothly with methanol "or ethanol# to give the enaminal "61# "Equation "002##
ð57AG"E#359\ 58HCA1530Ł[
H O
N MnO2
OH
+ N (112)
86%
O
O MeOH MeO
(113)
Me2N 92%
Me2N
(71) (72)
Photolysis of isoxazilines such as "62# "Equation "003## has been shown to lead to the formation
of b!nitrogen substituted a\b!unsaturated aldehydes "63# ð62TL1172\ 64T0262\ 66H"5#0448\ 73JCS"P0#1092\
75CCC1056Ł[
Ph Ph Ph Ph
hν, MeCN
(114)
N 86% NH2
O O
(73) (74)
Sodium azide reacts with the chlorinated cycloalkenal "64# to give the azidocycloalkenal "65#
without cyclisation to the isoxazole as expected "Equation "004## ð77SC0364Ł[
CHO CHO
NaN3, DMSO
(115)
80%
Cl N3
(75) (76)
CO, Rh4(CO)12 R1 R2 R2 R1
R1 R2 + (116)
PhH, Et3N, 100 °C
OHC SiMe2Ph OHC SiMe2Ph
PhS OMe
TMS
(77)
pcc
HO TMS TMS
OHC (117)
CH2Cl2
67%
(78) (79)
Me3Sn CHO
(Me3Sn)2, Pd(Ph3P)4, THF
R1 CHO (118)
R1
(80)
(CO)5Mn CHO
CHO + HMn(CO)5 (119)
(81)
OH MnO2, 20 °C O
(120)
S S 65% S S
OH Ni2O3, 20 °C O
(121)
Ph 70% Ph
O
i, Ph2P O
2 O
N ii, H+
(122)
H 59%
a\b!Triple Bond 68
Alkynals can be prepared simply by the formylation of acetylide anions\ and this has been
reported using a formate ester or DMF ð47JCS0943\ 67S296Ł[ Terminal alkynes can also be formylated
under acidic conditions using an ortho!ester in the presence of a Lewis acid catalyst at high
temperature "Equation "012## ð52OSC"3#790Ł[ Eliminations of HBr from 1\2!dibromoaldehydes lead
to alkynals in moderate yield ð34OS"14#81Ł\ as does the reaction of formyl phosphorane with acid
chlorides followed by elimination of triphenylphosphine oxide ð74S048Ł[
i, ZnI2, 214 °C
ii, 7% H2SO4, 100 °C
Ph + HC(OEt)3 Ph CHO (123)
64%
Copyright # 1995, Elsevier Ltd. All R ights Reserved Comprehensive Organic Functional Group Transformations
OFA038
3.03
Aldehydes: Aryl and Heteroaryl
Aldehydes
GREGORY J. HOLLINGWORTH
University of Nottingham, UK
2[92[0 GENERAL METHODS FOR THE SYNTHESIS OF ARYL ALDEHYDES 71
2[92[0[0 Reduction of Aromatic Carboxylic Acids and Their Derivatives 71
2[92[0[0[0 Reduction of benzoic acids 71
2[92[0[0[1 Reduction of benzoyl halides 72
2[92[0[0[2 Reduction of aromatic esters 73
2[92[0[0[3 Reduction of anhydrides 73
2[92[0[0[4 Reduction of thiol esters 74
2[92[0[0[5 Reduction of amides 74
2[92[0[0[6 Reduction of aromatic nitriles 75
2[92[0[1 Oxidation of Aromatic Methyl Groups and Benzyl Alcohols\ Halides and Amines 75
2[92[0[1[0 Oxidation of toluenes to benzaldehydes 75
2[92[0[1[1 Oxidation of aryl ethylenes 76
2[92[0[1[2 Oxidation of benzylic alcohols 76
2[92[0[1[3 Oxidation of benzyl halides 77
2[92[0[1[4 Oxidation of benzylamines 78
2[92[0[2 Synthesis of Benzaldehydes from Aryl Or`anometallic Rea`ents 78
2[92[0[2[0 Aryl palladium rea`ents 78
2[92[0[2[1 Aryl lithium rea`ents and aryl Gri`nard rea`ents 89
2[92[0[3 Other Formylation Reactions of Arenes 80
2[92[0[3[0 The Duff reaction 80
2[92[0[3[1 The ReimerÐTiemann reaction 80
2[92[0[3[2 The VilsmeierÐHaack reaction 80
2[92[0[3[3 The GattermannÐKoch reaction 81
2[92[0[3[4 The Gattermann reaction 81
2[92[0[3[5 Dichloromethyl methyl ether as formylation rea`ent 81
2[92[0[3[6 Miscellaneous formylations 82
70
71 Aryl and Heteroaryl Aldehydes
2[92[3[2[0 Pyrrole and indole carboxaldehydes 095
2[92[3[2[1 Pyridine and quinoline carboxaldehydes 096
2[92[3[3 Miscellaneous Heterocycles] Oxazoles\ Thiazoles and Imidazoles 098
CO2H CHO
t-hexBHBr•SMe2
(1)
90%
H2N H 2N
Since diisobutylaluminum hydride "dibal!H# was _rst observed to reduce acids to aldehydes
ð53ZOB0918Ł\ a variety of aluminum!based reagents have been used for this transformation[ Benzoic
acid itself has been reduced by bis"N!methylpiperazinyl# aluminum hydride in 75) yield ð63CL0336\
73JOC1168Ł[ Other suitable reducing agents include lithium tris"dialkylamino# aluminum hydrides
ð81MI 292!90Ł and bis"dialkylamino# aluminum dihydrides ð83MI 292!90Ł[
Treatment of simple benzoic acids with certain hypervalent silicon species leads to a silyl carboxy!
late\ which on pyrolysis gives aldehydes in moderate to good yields "49Ð85)# "Equation "1##
ð76TL2830Ł[ Sato|s titanium!catalysed Grignard reagent method tends to over!reduce aromatic acids
ð70S760Ł[ Aromatic acids also react with oxalyl chloride:DMF to form carboxymethylene iminium
chlorides\ which can then be reduced in situ with LiAlH"OBut#2 and a CuI catalyst to aldehydes in
moderate yield "Scheme 0# ð72TL0432Ł[
General Methods 72
Ph NMe2
SiH2
i,
CO2H CHO
ii, heat
(2)
F 94% F
O
CO2H CHO
(COCl)2 + Me LiAlH(OBut)3
O N
DMF CuI
O2N Me O2N
O 2N
Scheme 1
Other less widely used reducing methods include the use of sodium amalgam ð35JA1491Ł and
electrochemical reduction ð61JOC0402\ 83CPB093Ł[
An indirect method of reduction involves treatment of the carboxylic acid with a dithiaborinane
reagent ð76JOC1003\ 76PAC0994\ 76TL0802Ł^ the product dithioacetals are then readily hydrolysed to
the corresponding aldehydes[
COCl CHO
NaAlH(OBut)3
(3)
88%
OMe OMe
Benzoyl bromide may be cleanly reduced to benzaldehyde by tributylstannane ð55JA460Ł\ but this
reducing agent works well for chlorides only if a palladium catalyst\ normally Pd"PPh2#3\ is present
giving high yields of simple benzaldehydes "Equation "3## ð79CC321\ 70JOC3328Ł^ tributyl!
germane:Pd"PPh2#3 has also been used ð78JOM"265#30Ł[ Triethylsilane may act as a reducing agent
in the presence of a palladium ð58JOC0866Ł\ platinum ð69CC0692\ 64JCS"D#1535Ł or a rhodium catalyst
ð64JCS"D#1359Ł[ The former procedure requires the least harsh reaction conditions\ whilst the latter
tends to produce signi_cant quantities of diaryl ketones in addition to the desired product[ Excellent
yields have been obtained using hypervalent silicon hydrides ð77TL0160Ł[ Some iron complexes
reduce aromatic acyl halides to aldehydes\ such as Collmans reagent\ Na1Fe"CO#3 ð60BCJ1458Ł and
the hydridoiron tetracarbonyl anion HFe"CO#3− ð66TL670\ 89CRV0930Ł[ Various other transition
metal complex reducing agents have also been used for this transformation ð73OM0590\
74JOM"181#114Ł[ Finally\ yields of over 79) for the reductions of aromatic acyl chlorides have
been reported using the heterocyclic hydride donor 0\2!dimethyl!1!phenyl benzimidazoline "DMBI#
"Equation "4## ð75JOC4399Ł[
73 Aryl and Heteroaryl Aldehydes
COCl CHO
Bu3SnH, Pd(PPh3)4
(4)
92%
Me
N
Ph
N
COCl Me CHO
MeCN, AcOH
(5)
85%
MeO MeO
CO2Et CHO
dibal-H
(6)
70%
MeO MeO
Moderate yields with simple benzoate esters have been achieved\ however\ with bis"3!methyl!0!
piperazinyl# aluminum hydride "BMPA# ð64CL104Ł[ Another reagent\ Red!Al "NaAlH1
"OC1H3OCH2#1#\ reduces aromatic esters in low yield ð69MI 292!90Ł\ but when an equivalent of
N!methylpiperazine is added to the Red!Al prior to the ester\ the modi_ed reagent produces benz!
aldehyde in 74) yield ð65S415Ł "isolated as its 1\3!dinitrophenylhydrazine "DNP##[ Two promising
reducing agents reported in the early 0889s\ for this transformation are sodium diethylpiperidino
aluminum hydride ð80MI 292!90Ł and lithium tris"diethylamino# aluminum hydride ð81OPP224Ł[
O O
– CHO
Na2Fe(CO)4 Fe(CO)4
O 2Na+
O–
CO2H
O O
(1)
Scheme 2
Mixed aryl and alkyl anhydrides show little selectivity as to which C0O bond is cleaved[ Related
aromatic carboxylic ethyl carbonic anhydrides\ however\ react to give moderate yields of simple
benzaldehydes ð64TL0952Ł[
Triphenylacetic benzoic anhydride on treatment with lithium metal gave complete selectivity\
with benzaldehyde being the only aldehyde product ð81TL2626Ł[ A similar result was observed for
the same substrate when the C0O bond was cleaved photochemically ð82JA71Ł[
General Methods 74
2[92[0[0[4 Reduction of thiol esters
Aromatic carboxylic acids have been converted into aldehydes in two steps via their thiol esters[
Hydrogenolysis of thiol esters in the presence of Raney nickel then produces the corresponding
aldehydes in moderate yields ð48CB429\ 43OR"7#107Ł[ The 1!thiazoline!1!thiol ester of benzoic acid
has been reduced to benzaldehyde in 82) yield by dibal!H ð67CC229Ł[ Other reducing agents for
aromatic thiol esters are lithium metal ð81TL2626Ł\ and triethylsilane in the presence of a catalytic
amount of palladium on carbon ð89JA6949Ł[ The latter method appears to tolerate a wide range of
functional groups including esters\ amides\ acetals and sul_des\ and has been used in many natural
product syntheses\ although the vast majority of reported cases are for aliphatic thiolesters[
N
N
(2)
Reductions of 2!acyl thiazolidine!1!thiones "2# with either dibal!H or lithium tri"t!butoxy# alumi!
num hydride give greater than 79) yield for benzaldehyde and p!chloro! and p!nitrobenzaldehydes
ð68BCJ444Ł\ and dibal!H also reduces the Weinreb amide N!methyl!N!methoxybenzamide "3# to
benzaldehyde in 60) yield ð70TL2704Ł[ Newer hydride reagents which reduce primary carboxamides
in good yield include lithium n!butyl diisobutyl aluminum hydride ð73JOC0606Ł and lithium tris!
"diethylamino# aluminum hydride ð80TL5892Ł[ The reduction of tertiary amides has also been
accomplished using ethyl tri~ate and L!selectride ð89JCS"P0#646Ł[
O S O
OMe
N N
S
Me
(3) (4)
For aromatic aldehyde syntheses some of the older methods are still amongst the best[ These
earlier methods have been reviewed ð43OR"7#107Ł[ 0!Aroyl!1!cyano!0\1!dihydroquinolines "or Reis!
sert compounds "4## are readily formed from acyl chlorides\ and may be hydrolysed under acidic
conditions to give good yields of benzaldehydes[ The McFadyen and Stevens procedure is a good
method for the preparation of benzaldehydes containing hydroxy\ alkoxy\ alkyl and halo substitu!
ents\ by basic decomposition of 0!acyl!1!arylsulfonylhydrazines "5#[ Alkoxy and alkyl benzaldehydes
have been prepared by the method of Sonn and Muller in moderate to good yields from
N!phenylaromatic amides in a three!step sequence via an imido chloride and Schi}s base[
75 Aryl and Heteroaryl Aldehydes
O
H
N CN N
Ar N SO2Ar
H
O Ar
(5) (6)
Inevitably newer methods have been developed using metal hydride reagents[ Dibal!H\ LiAlH3
and NaAlH3 reduce benzonitrile to benzaldehyde in 26)\ 81) and 89) yields respectively
ð48JOC516\ 53JA0968\ 82JOC3616Ł\ but a more general method uses Li"EtO#2AlH ð48TL8\ 53JA0974Ł[
Again alkyl\ alkoxy and halo substituents are tolerated[ More modern hydride reagents that have
been used for this transformation in high yield include t!hexylbromoboraneÐdimethyl sul_de com!
plex ð76MI 292!91Ł\ sodium diethylpiperidino hydroaluminate "SDPA# "Equation "6## ð82JOC0830Ł
and lithium tris"dihexylamino# aluminum hydride ð81MI 292!91\ 81OPP220Ł[ This latter reagent is
reported to leave aliphatic nitriles untouched[
O
CHO
Me SDPA
N (7)
99%
Me
A relatively mild two!step procedure which converts aromatic nitriles into benzaldehydes involves
alkylation of the nitrogen of the CN bond to _rst form the activated N!alkylnitrilium ion "7#\ which
is then reduced in good yield by triethylsilane to the N!alkylaldimine^ hydrolysis _nally gives the
aldehyde[ Alkylation of the nitrile can be accomplished with either triethyloxonium tetra!
~uoroborate\ or with isopropyl chloride in the presence of FeCl2 ð63CC34\ 70JOC591Ł[ Alkyl\ alkoxy\
halo and notably nitro and carbethoxy substituents are tolerated[
+
Ar N R
(8)
Aromatic aldehydes have also been produced by reactions of nitriles with Raney nickel in
re~uxing aqueous HCO1H ð54JCS4664Ł and\ in 0878\ in excellent yields\ by wet Raney nickel using
triethylammonium hypophosphite hydrate as a hydrogen source[ Under these controlled conditions
hydrogenation of the nitrile is facile\ but hydrolysis of the product imine predominates over
hydrogenation\ thus leading to the aldehydes with little or no over!reduction ð78JOC838Ł[
2[92[0[1 Oxidation of Aromatic Methyl Groups and Benzyl Alcohols\ Halides and Amines
O O
MeO
MeO
CN
CN i, O3 N
N MeO CHO (9)
MeO
ii, Me2S
Perhaps a more synthetically useful procedure than oxidative cleavage of simple styrenes is the
ozonolysis of benzofurans to 1!hydroxy benzaldehydes ð82CPB0055Ł[ This strategy was used by
Gammill and co!worker\ who treated khellin with OsO3:NaIO3 and produced the hydroxy benz!
aldehyde in 62) yield\ which was then used in the synthesis of various khellin analogues "Equation
"09## ð73TL1842\ 75JOC2005Ł[
OMe O OMe O
OHC
OsO4, NaIO4, THF, 50 °C
(10)
O O HO O
OMe OMe
CHO
Br [Me2CNO2]– Na+
(13)
Br 75%
Br
Other reagents which have been used for the oxidation of benzyl halides to benzaldehydes include
various amine oxides\ particularly pyridine N!oxide ð46JOC0024Ł\ dimethylaminopyridine N!oxide
ð70BCJ1110Ł and N!methylmorpholine N!oxide ð81SC0856Ł[ McKillop et al[ have reported the reac!
tion between various benzyl bromides and mercury"I# nitrate which leads to nitrate esters\ which
then decompose to benzaldehydes on treatment with aqueous ethanolic alkali\ for example\ Equation
"04# ð63SC34Ł[ Finally\ a whole host of chromium!based oxidants e}ect the transformation ð65CC089\
65TL2874\ 78BSB110\ 81SC0380\ 82BSB188Ł^ see also ð67S508Ł[
Cl Cl
i, Hg2(ONO2)2, DME
ii, NaOH (aq.), EtOH CHO
Br (15)
71%
Cl Cl
I CHO
CO, Bu3SnH, THF, Pd(PPh3)4 (cat.)
(16)
91%
MeO2C MeO2C
89 Aryl and Heteroaryl Aldehydes
Aryl halides have been converted into their aldehydes in similar palladium!catalysed reactions
using dihydrogen to reduce the intermediate acyl palladium complex[ However\ the shortfall of this
method is the high pressure required for reaction "7[2 MPa "0199 psi## ð63JA6650Ł[ Use of poly
"methylhydrosiloxane# as hydrogen donor allows the reaction to be carried out under the reduced
pressure of 49 psi ð73JOC3998Ł\ but the practical ease of the Stille procedure makes it more generally
useful[ Various other palladium!catalysed formylations are known ð65BCJ0570\ 73JOM"169#172\
78CC0705Ł\ with some starting from aryl diazonium salts[
Carbonylations of aryl halides under radical conditions have also been accomplished\ although
once again high pressures of CO are required ð89TL5776Ł[
Br CHO
Li, DMF, ultrasound, THF
(17)
81%
+ O
Me Ac
N N
N+ I–
I–
Me
(9) (10)
Various arenes may be deprotonated adjacent to certain existing functionality capable of sta!
bilising the anion formed\ that is\ directed metallation groups "DMGs#[ The resulting aryl lithium
reagents can then be formylated using one of the agents described above\ normally DMF[ The
products are thus 1!substituted benzaldehydes[ There are a vast number of DMGs "for excellent
reviews see ð68OR"15#0\ 77BSF56Ł# and an {order of metallation| has been established for these groups[
Most appear applicable to the synthesis of benzaldehydes especially the alkoxy function\ for example\
Equation "07# ð68S895Ł[ For a later example see ð82T0310Ł[
O OMe O OMe
i, BunLi
(18)
ii, DMF CHO
OMe OMe
Other important DMGs that have been applied to the synthesis of benzaldehydes include t!butyl
sulfonyl ð78JOC13Ł\ tertiary amido ð71ACR295Ł\ and ~uoro groups ð81TL6388Ł[
General Methods 80
2[92[0[3 Other Formylation Reactions of Arenes
CHO
HMT, TFA, reflux, 12 h
(19)
HO 95% HO
NaOH, CHCl3 N
N (20)
HO O
HO O 40%
CHO
O O
MFA, POCl3
O O (22)
63% CHO
OMe OMe
81 Aryl and Heteroaryl Aldehydes
Other acid chlorides have also been used\ including thionyl chloride\ oxalyl chloride\ phosgene\
phosphorus pentoxide\ phosphorus tribromide\ phosphorus pentachloride and pyrophosphoryl
chloride[ In the last example a more reactive electrophilic species serves as formylating agent\ and
higher yields and regioselectivity than normal have been observed "Equation "12## ð81SL66\ 82T3904Ł[
OMe OMe
P2O3Cl4, DMF OHC
(23)
100%
OMe OMe
Another modi_cation\ which leads to improved yields for less active substrates\ makes use of the
reactive iminium salt produced from tri~uoromethane sulfonic anhydride and DMF ð89CC0460Ł[
An indirect method for the preparation of benzaldehydes under Vilsmeier conditions has
been developed using aryl trialkylstannanes[ Thus treatment of trimethylphenylstannane with
POCl2:DMF at room temperature gives 45) benzaldehyde via electrophilic ipso!substitution with
loss of a stannyl cation ð78T840Ł[
OHC
Zn(CN)2, HCl, Et2O
O (24)
HO HO O
87%
OMe OMe
MeO Cl OMe
MeO
Br , CH2Cl2, SnCl4 Br
Cl
N OHC N (25)
82%
OMe OMe
O O
Benzaldehyde and Substituted Benzaldehydes 82
2[92[0[3[6 Miscellaneous formylations
Various miscellaneous formylations of arenes are known[ Of these\ among the more important
are the formylations of simple nonactivated arenes with formyl ~uoride ð59JA1279\ 76CRV560Ł in a
FriedelÐCrafts type reaction[ Similar\ simple arenes have also been formylated with CO\ catalysed
by super acids\ where yields are moderate ð76CRV560\ 80CC0440\ 81JOC1566Ł[ For a detailed discussion
of formylation reactions in general\ see ðB!53MI 292!90Ł[
The formation of benzaldehydes directly by pericyclic reactions is rare and is not discussed in this
chapter[
2[92[1[0 Benzaldehyde
Although\ virtually all of the reductive\ oxidative and organometallic routes mentioned in Section
2[92[0 give good yields of benzaldehyde\ not all of the formylation methods are generally applicable
since most require activating electron!donating substituents on the substrate[ The RiemerÐTiemann
reaction is not applicable and the VilsmeierÐHaack reaction also fails for benzene[ The Gattermann
reaction\ Du} reaction and reaction of benzene with dichloromethyl methyl ether:AlCl2 all give
poor yields of benzaldehyde[ Formylation of benzene using formyl ~uoride with boron tri~uoride as
catalyst proceeds in modest yield "45)# ð76CRV560Ł[ Best results are obtained using the GattermannÐ
Koch procedure with AlBr2 as catalyst "89) yield of benzaldehyde# ðB!53MI 292!90Ł[
An industrially viable route to benzaldehyde involves the oxidation of toluene using chlorine
followed by hydrolysis of the benzal chloride intermediate\ although some ring chlorination products
are also observed[ An alternative\ cleaner method is oxidation of toluene using manganese dioxide
in the presence of acetic anhydride[ In this case the intermediate is benzal diacetate which is also
readily hydrolysed to benzaldehyde ðB!78MI 292!91Ł[
CN CHO
Li(OEt)3AlH, Et2O
(26)
87%
Virtually all of the methods listed for the oxidations of benzyl alcohols\ halides and amines to
benzaldehydes appear to tolerate alkyl substituents on the benzene ring\ and they are used exten!
sively[ The same applies to the organometallic methods[ The palladium!catalysed formylation of
aryl iodides is reported to give lower yields for the formation of 1!substituted benzaldehydes than
for 2! or 3!substituted analogues\ presumably due to steric hindrance ð75JA341Ł[ This may be true
for other methods\ but few comparative studies have been reported[
Alkyl benzenes are signi_cantly more reactive towards formylation than benzene itself[ Of the
formylation methods\ the GattermannÐKoch reaction of alkyl benzenes is suitable for the formation
of para!substituted benzaldehydes ðB!53MI 292!90Ł[ Only modest yields result\ but the reaction does
give almost exclusively the one isomer[ Formyl ~uoride formylations also give high paraÐortho
ratios and better yields "×69)# for alkyl and polyalkyl benzenes\ for example\ Equation "17#
ð76CRV560Ł[
CHO
HCOF, BF3
(28)
72%
The modi_ed Du} reaction gives moderate yields of alkyl benzaldehydes\ although mixtures of
ortho! and para! products are generally observed[ However\ in some cases where steric hindrance
plays a role\ good yields of a single product may be achieved\ for example\ t!butyl benzene gives a
64) yield of 3!t!butyl benzaldehyde ð61JOC2861Ł[ The Gattermann synthesis works best for very
activated aryls but also works for alkylbenzenes at elevated temperatures[ Yields are often good[
An example by a modi_ed procedure using s!triazine instead of zinc cyanide is shown in Equation
"18# ð58AP"291#717\ 60AP"293#251Ł^ para! or ortho!substitution is observed[
N CHO
N N , HCl
(29)
89%
Dichloromethyl alkyl ethers may also be used for the synthesis of alkyl benzaldehydes\ although
the regioselectivity is not as good as for many other formylations\ so this method is most useful if
one position is blocked[
2[92[1[2 Halobenzaldehydes
The hydrogenolysis of organic halides\ including aryl halides is a well!documented reaction
ð79S314Ł\ and hence caution should be exercised when synthesising halobenzaldehydes by reductions
of corresponding halo benzoic acid derivatives\ especially since the presence of the electron!with!
drawing acyl group makes this process more facile[ Nevertheless\ many of the reductive methods
are applicable\ notably those using borane reagents and certain aluminum hydrides[ Some examples
giving good yields of halobenzaldehydes are the reduction of halobenzoic acids with NaAlH"ButO#2
ð82JOC3621Ł and t!thexylbromoborane!DMS complex ð76JOC4929Ł\ reduction of halo!substituted
benzoyl chlorides with complex borohydrides ð67TL1362Ł\ and the reduction of halobenzonitriles
with LiAlH"EtO#2 "Equation "29## ð53JA0974Ł[
Benzaldehyde and Substituted Benzaldehydes 84
CN CHO
LiAlH(OEt)3
(30)
84%
Cl Cl
CO2H CHO
(32)
96%
F F
A halo!substituent appears to be inert to virtually all the methods of oxidising benzyl alcohols\
halides and amines\ thus making it an excellent method for the synthesis of halobenzaldehydes[
Furthermore\ the slight electron!withdrawing e}ect exhibited by these substituents helps prevent
over!oxidation[ Similarly\ halotoluenes can be oxidised e.ciently to benzaldehydes by the methods
described in Section 2[92[0[1[0[ For examples see Equation "22# ð89BSB234Ł\ Equation "23# ð78S182Ł
and Equation "24# ð63SC34Ł[
CHO
NH2•HBr Me2SO, 100 °C
(33)
Cl 87%
Cl
CHO
Br i, Hg2(ONO2)2, DME
(35)
Br ii, NaOH
Br
Of the organometallic!based methods for the synthesis of benzaldehydes\ many utilise haloarenes
as starting materials[ The e.ciency of metalÐhalogen exchange varies in the order I×Br×Cl×F\
and thus selective formylations of dihaloarenes are possible[ This strategy has been utilised suc!
cessfully for the synthesis of Br!\ Cl! and F!substituted benzaldehydes[ Methods which have been
used include Grignard reagent additions to imidazolidinium salts "Equation "25## ð68CC006Ł\ pal!
ladium!catalysed formylations with CO and either Bu2SnH "Equation "26## ð75JA341Ł or poly"methyl
hydrosiloxane# "PMHS# "Equation "27## ð73JOC3998Ł[
Me +
N
N Ac
i, I–
MgBr CHO
ii, H2O
(36)
90%
Cl Cl
I CHO
CO (3 atm), Bu3SnH, Pd(PPh3)4, THF
(37)
78%
Cl Cl
85 Aryl and Heteroaryl Aldehydes
I CHO
CO (50 atm), PMHS, Pd(PPh3)4
(38)
95%
Br Br
Cl Cl
i, LDA
I ii, DMF I CHO
(39)
97%
F F
Classical formylations of simple haloarenes to give halobenzaldehydes are not widely used since
halo substituents deactivate the ring towards electrophilic substitution[ However\ if other activating
groups are present\ halo groups are tolerated in many cases[
COCl CHO
(Ph3P)2CuBH4, PPh3, Me2CO
(40)
MeO 86% MeO
OMe OMe
By contrast\ hardly any examples have been reported for reductions of benzoic acids containing
a free hydroxy group[ One method that has been used\ however\ is reduction by sodium amalgam
"Equation "30## ð35JA1491Ł[
CO2H CHO
Na-Hg
(41)
OH 57% OH
F F
Most oxidative methods also tolerate alkoxy groups\ and more examples containing free hydroxy
groups are found using these reactions^ see Equation "31# ð68S033Ł\ Equation "32# ð82TL2408Ł and
Equation "33# ð73S636Ł[
OHC
ddq, dioxan
(42)
O 70% O
OMe O OMe O
Ag2CO3, DMSO, 90 °C
(43)
O Ph 80% O Ph
CHO
OMe Br O OMe O
Benzaldehyde and Substituted Benzaldehydes 86
OH CHO
Me2SeO, PhH, 80 °C OH
OH (44)
92%
OH CHO
Aryl Grignard reagents containing alkoxy substituents have been formylated using reagents
such as DMF "Equation "34## ð66JOC2297Ł\ lithium formate ð73TL0732Ł and N!3\3!trimethyl!1!
oxazolinium iodide ð69JA5565\ 63OS"43#31Ł\ and Stille!type formylations of methoxy!substituted iodo!
benzenes have also been accomplished ð75JA341Ł[
Br CHO
i, Mg
(45)
ii, DMF
MeO MeO
Oxygen is one of the most widely used atoms for directed ortho!metallations[ This method has
been utilised extensively for the selective conversion of oxygen substituted arenes into ortho!oxygen
substituted benzaldehydes[ Some examples are shown in Equation "35# ð82T0310Ł and Equation "36#
ð80SC056Ł[ Selective ortho!formylations of phenols may be realised by reaction of the corresponding
aryloxymagnesium halides with formaldehyde in the presence of HMPA "Equation "37##
ð67JCS"P0#207Ł[ For other less direct methods for overall exclusive ortho!formylation of phenols\
see ð63TL2352Ł[ RiemerÐTiemann\ Vilsmeier\ Gattermann and Lewis acid mediated reactions of
dichloromethyl ethers are all particularly well suited to substrates containing electron!donating
substituents such as hydroxyl and alkoxy groups\ and they have been used extensively "see Section
2[92[0[3#[ Some further examples containing various other functional groups are shown in Equation
"38# ð89SC598Ł\ Equation "49# ð76TL1362Ł and Equation "40# ð72CPB0640Ł[
i, BunLi
O
O ii, DMF
iii, H+
(46)
72% O O-THP
O O-THP
CHO
i, BunLi
MeO O-TIPS MeO OH
ii, DMF
iii, H+
(47)
85% OHC
OMe OMe
OH OH
NaOH, CHCl3, H2O, ultrasound
(49)
84%
Cl Cl CHO
O Cl O
OMe
Cl
MeO N MeO N (50)
TiCl4, CH2Cl2
O O
MeO MeO CHO
OH OH
MeO2C MeO2C CHO
HMT, MeSO3H, HCl, H2O
(51)
77%
Cl Cl
87 Aryl and Heteroaryl Aldehydes
An alternative formylation procedure for arenes containing oxygen substituents is by reaction
with tris"phenylthio#methane in the presence of dimethyl"methylthio#sulfonium tetra~uoroborate
"dmtsf#[ The intermediate dithioacetals formed in these reactions are readily hydrolysed to produce
the corresponding benzaldehydes\ for example\ Scheme 2 ð73S055Ł[
OMe OMe
OMe
DMTSF, (PhS)3CH DMTSF, H2O
OMe 70%
OMe
OMe
PhS SPh CHO
Scheme 3
SMe SMe
Me2SeO, ClCH2CH2Cl, KHPO4
(52)
Br 97%
CHO
i, BunLi SO2But
SO2But ii, DMF
(53)
90%
CHO
i, BunLi SO3Et
SO3Et
ii, DMF
(54)
74%
CHO
Very few methods have been reported for the formylation of aryl alkyl thioethers by classical
formylation techniques[ Vilsmeier reaction of methyl phenyl sul_de does give 3!methyl!
thiobenzaldehyde but the yield is reported to be poor ð44BSF0483Ł[
Fewer examples of reductive approaches to amino benzaldehydes are reported\ although good
yields have been found for the reductions of nitrobenzoic acids by t!thexylbromoborane!DMS
complex ð76JOC4929Ł\ or ButLi:8!BBN!H ð76TL5120Ł[
The nitro substituent appears to tolerate most oxidation procedures\ with excellent yields being
obtained for the oxidation of 3!nitrobenzyl bromide with dimethyl selenoxide "099)# ð73S636Ł\ or
the oxidation of 3!nitrobenzyl alcohol with tetrakis"pyridino# cobalt"II# dichromate "84)#
ð81SC0380Ł^ see also ð89BCJ1322Ł[ Free amino substituents do not appear to tolerate many oxidants\
although amino toluenes have been oxidised by 1\2!dichloro!4\5!dicyano!0\3!benzoquinone "ddq#
if the amino group is sterically hindered "Equation "45## ð73TL1890Ł[
CHO
ddq, dioxan
(56)
H 2N 49% H2N
The strong electron!withdrawing nature of the nitro group actually makes nitroarenes susceptible
to nucleophilic substitution\ and direct formylations have been achieved by reactions with the CCl2−
anion followed by hydrolysis of the intermediate "Scheme 3# ð76TL2910Ł[
Cl
Cl Cl CHO
ButOK, CHCl3 Cl H+, H2O
Cl
94% 66%
NO2 NO2
NO2
Scheme 4
Formylations of N!alkyl and N\N!dialkyl amines are best achieved using the Vilsmeier reaction\
although yields are very variable^ the formylations occur para to the amine substituent ð52OSC"3#220\
B!53MI 292!90\ 82T3904Ł[
Finally a simple direct route to 3!aminobenzaldehydes has been achieved by reaction of simple
anilines with the DMSO!HCl reagent in the presence of copper"II# chloride\ where yields are good
to excellent\ for example\ Equation "47# ð81JCS"P0#1124Ł[
Br Br
Br DMSO-HCl, CuCl2 Br CHO
(58)
84%
H2N H 2N
OMe
OMe OMe
Na2CO3
OMe (59)
O 79%
PhSO2 N OHC
N
A greater variety of polyaromatic aldehydes have been made by oxidative routes[ Oxidants
that have been used include barium manganate "Equation "59## ð67TL728Ł\ ddq "Equation "50##
ð77JOC3476Ł and N!cyclohexylbenzene sul_namide "Equation "51## ð70JOC3506Ł[
CHO
OH BaMnO4, CH2Cl2
(60)
OH 87%
CHO
Br Br
NaH CHO
Br (62)
O
S Ph
N
H
Br CHO
Certain polyaromatic compounds on treatment with strong oxidants can be cleaved selectively at
one position to give aldehyde products\ for example\ Equation "53# ð59JOC0785Ł[
i, OsO4
ii, NaIO4
(64)
78% CHO
CHO
Polyaromatic Aldehydes 090
Naphthyl lithium and naphthyl magnesium halide reagents can be formylated by dialkyl!
formamides\ or by other formylating agents mentioned in Section 2[92[0[2^ see for example ð67S392\
70AG"E#767\ 73S117\ 73TL0732Ł^ yields are generally high[
Many polyaromatic aldehydes have been made by classical electrophilic!substitution reactions of
activated arenes with formyl cation equivalents[ In these reactions regioselectivity is an important
factor[ Formylation of naphthalene generally occurs at the 0!position\ as is the case using dichloro!
methyl methyl ether:SnCl3[ The yield in this case is 79) ð59CB77Ł[ Anthracene gives an 73) yield
of 8!formyl anthracene in the Vilsmeier reaction "Equation "54## ð44OSC"2#87Ł[
CHO
PhMeNCHO, POCl3
(65)
84%
Anthracene itself has also been formylated in nearly quantitative yield by a modi_ed Vilsmeier
reaction using the formylation complex derived from tri~uoromethane sulfonic anhydride and DMF
ð89CC0460Ł[ Naphthalenes with electron!donating substituents in the 1!position formylate in the
0!position of the same ring as the activating substituent "Equation "55# ð61JCS"P0#781Ł and Equation
"56# ð52CB297Ł#^ similar substituents on anthracenes alter the position of formylation "Equation
"57## ð45MI 292!90\ 63BCJ0576Ł[
CHO
Zn(CN)2, AlCl3, HCl
(66)
89%
Cl
CHO
OH OMe, TiCl4
Cl OH
(67)
82%
CHO
OH
Zn(CN)2, HCl, Et2O, H2O OH
(68)
OMe OMe
OMe OMe
CHO OMe
(11)
091 Aryl and Heteroaryl Aldehydes
2[92[3 HETEROCYCLIC ARYL ALDEHYDES
Furans and benzofurans appear to tolerate many oxidative conditions and these methods have
proved popular for the synthesis of a variety of O!hetaryl aldehydes[ Oxidants that have been used
include MnO1 "Equation "60## ð60AJC0772Ł\ silver carbonate "Equation "61## ð65JHC414Ł\ or barium
ferrate "Equation "62## ð77BCJ1074Ł for the oxidation of hydroxymethyl furans[ Oxidations under
Swern conditions have been carried out in the presence of a phenythio methyl group in good yield
"Equation "63## ð81JA2809Ł[
OMe OMe
OH MnO2, CCl4
(71)
87% CHO
O O
Ag2CO3, PhH
OH (72)
O 80% O CHO
HO OH OHC CHO
BaFeO4, H2O, PhH
(73)
Ph Ph 80%
O Ph O Ph
CO2Me CO2Me
i, (COCl)2, DMSO
HO SPh SPh (74)
ii, Et3N OHC
O O
Furans containing halomethyl substituents have been oxidised to the corresponding aldehydes
by\ amongst others\ the Sommelet reaction\ for example\ Equation "64# ð69BSF0334Ł\ or by oxidation
with the sodium salt of 1!nitropropane\ for example\ Equation "65# ð57JHC84Ł[
CO2Et CO2Et
NaOEt, PriNO2, EtOH
Br (76)
CF3 71% OHC CF3
O O
Heterocyclic Aryl Aldehydes 092
Other oxidative methods leading to furan carboxaldehydes include oxidative decarboxylation of
a benzofuran!2!acetic acid using pyridine N!oxide "Equation "66## ð81IJC"B#415Ł\ and a!sulfuration
of a phenylthiomethyl group followed by silver perchlorate promoted hydrolysis of the intermediate
dithioacetal "Equation "67## ð81JA2809Ł[ This latter example has been used in studies towards the
total synthesis of furanocembranolides[ A _nal oxidative procedure involves cleavage of a diol using
an oxidant such as NaIO3\ for example\ Equation "68#[ The substrate in this case is readily available
by condensation of glucose with acetylacetone ð34JCS005Ł[
+
N O–
CO2H CHO
Ac2O, PhH
(77)
90%
O O
CO2Me CO2Me
CHO
SPh
O i, KHMDS, then PhSO2SPh O
(78)
ii, AgClO4, H2O, PhH
O O
OSiButPh2 OSiButPh2
O H O H
OH OH O
HO O
NaIO4
(79)
OH O
OHC O
Lithiations of furans and benzofurans occur preferentially at the 1!position[ This strategy has
been used in the synthesis of the corresponding 1!formyl derivatives by quenching the anions
with DMF\ for example\ Equation "79# ð66BSF031Ł^ see also ð67HCA329\ 72TL0666Ł[ MetalÐhalogen
exchange reactions followed by quenching with DMF have also been used for the synthesis of
both 1! and 2!furan carboxaldehydes\ for example\ ð69BSF0727Ł[ Preferential metallation of
1\2!dibromofuran occurs at the 1!position "Equation "70##[
BunLi, DMF
CHO (80)
O 70% O
Br Br
BunLi, DMF
(81)
O Br O CHO
Palladium!catalysed formylation of 2!iodofuran with CO and Bu2SnH occurs under Stille con!
ditions in 59) yield ð75JA341Ł[ Classical formylations of furans and benzofurans have been
accomplished using either Lewis acid mediated reactions with dichloromethyl methyl ether or by
Gattermann reactions[ The most popular method however is by use of the Vilsmeier reaction
ðB!53MI 292!90Ł[
Furans undergo formylation at the 1! or 4!positions\ and benzofurans at the 1!position pref!
erentially[ Formylation at other positions may occur if the favoured positions are blocked however\
although yields tend to be lower[ For benzofurans where the 1!position is blocked formylation in
the benzene ring may compete\ particularly if electron!donating substituents are present[ Selected
examples are presented in Equation "71# ð73JOC1404Ł\ Equation "72# ð42JIC092Ł and Equation "73#
ð81T0928Ł[ In the last example\ concomitant removal of the acetate function has been observed[
POCl3, DMF
(82)
96% CHO
O O
093 Aryl and Heteroaryl Aldehydes
O CHO
OMe OMe
NR2 H+
+ N O•
CHO
N2 O
H+
Me2CO
O H O
BF4–
O
Scheme 5
Br
CHO
Br2, AIBN, hν, CCl4 Br Na2CO3, py
Cl 85% 70% Cl
S Cl S
S
Scheme 6
Probably the most popular method for the synthesis of formyl thiophenes is by treatment of an
appropriate lithiated thiophene with a dialkyl formamide[ 1!Lithio thiophenes can be formed directly
from deprotonation of the parent thiophene or by haloÐlithium exchange from a 1!halothiophene\
for example\ ð42JA2586\ 65BSF154\ 77S205Ł[ The selective formation of 2!formyl thiophenes has also
been accomplished by haloÐlithium exchange of 2!bromothiophenes\ followed by addition of DMF\
for example\ Equation "75# ð56BSF1384\ 75CB2087Ł[
Br S i, BunLi CHO S
ii, DMF
(86)
99%
S S
Thiophene\ like furan is more reactive towards electrophiles than benzene[ Because of its
relatively high aromatic character\ substitution products predominate over addition products^ thus
thiophene is an excellent candidate for formylation by the Vilsmeier reaction ð49JA0311\ 52OSC"3#804\
B!53MI 292!90\ 79S022Ł[ Finally\ 1!nitrothiophene undergoes nucleophilic substitution with CCl2−
anion to give\ after hydrolysis\ the 2!formyl derivative ð76TL2910Ł[
The preparations of formyl benzothiophenes may be accomplished in many cases by analogous
procedures to those used for formyl thiophenes[ Lithiation occurs preferentially at the 1!position
and 2!formyl derivatives may be made by lithiation of the corresponding bromides\ for example\
Equation "77# ð60JCS"C#071Ł[ It should be noted however that 2!lithio benzofurans need to be kept
at low temperature to avoid ring cleavage occurring[
Benzothiophene is slightly less reactive towards electrophiles than thiophene itself\ but still
undergoes Vilsmeier formylation[ The 2!position is more activated than the 1!position\ unlike
thiophene and benzofuran\ although mixtures are often produced[ If one position is blocked single
products can be obtained\ for example\ Equation "78# ð56JCS"C#668Ł[ If the benzene ring contains
electron!donating substituents "or the heterocyclic ring contains electron!withdrawing substituents#\
then formylation may occur preferentially in the six!membered ring\ for example\ Equation "89#
ð56JCS668Ł[
OMe OMe
MFA, POCl3
(89)
50% CHO
S S
095 Aryl and Heteroaryl Aldehydes
OMe
OMe
MFA, POCl3
(90)
70% S
S
CHO
CO2Me CO2Me
MeO2C MeO2C
O O
Pyrrole and indole carboxaldehydes have been made from oxidations of their methyl analogues\
for example\ N!protected 2!methylindoles have been oxidised to the 2!carboxaldehydes by selenium
dioxide ð72TL3462Ł\ and 1!methylpyrroles have been oxidised by sulfuryl chloride ð63JOC1761Ł[ For
examples of the oxidation of 1!hydroxymethyl indoles to aldehydes by MnO1\ see ð73JOC2084\
76JCS"P0#820Ł^ the same reagent has also been used for the partial oxidation of 3!hydroxymethyl
indole ð79JOC2249Ł[ The Sommelet oxidation can be applied to indole systems ð41JA4009Ł\ and
N!protected pyrroles and indoles both metallate preferentially at the 1!position^ the anions may
then be quenched by DMF to give the aldehyde products ð71SC120\ 81H"23#0184Ł[
Probably the most frequently used way of making pyrrole or indole carboxaldehydes is by classical
formylation procedures[ The Vilsmeier reaction of pyrrole is a very important reaction and occurs
at the 1!position in good yield ð52OSC"3#720Ł[ If both of the 1! and 4!positions are blocked\ the other
positions often still undergo formylation ð52JOC2941Ł[ With electron!withdrawing groups in the
Heterocyclic Aryl Aldehydes 096
1!position\ formylation tends to occur at the 3!position[ However\ di}erent methods may give
di}erent selectivities[ For the reaction shown in Equation "82#\ the Vilsmeier procedure gave a
mixture of isomers in moderate yield\ whereas formylation with dichloromethyl methyl ether proved
far superior ð67JOC3738Ł[ If electron!donating groups are present in the 1!position 4!formyl deriva!
tives are generally observed[
OHC
OMe AlCl3, Cl2CHOMe
OMe (93)
N
O 89% N
Me O
Me
Indole\ unlike pyrrole\ but similar to benzothiophene undergoes preferential formylation at the
2!position[ Under Vilsmeier conditions 2!indole aldehyde itself is produced in 86) yield from indole
ð52OSC"3#428Ł[ If the 2!position is blocked\ 1!formylation is sometimes successful as shown in
Equation "83# ð74TL1044Ł[ If the nitrogen centre is not protected N!formylation tends to occur[
F F
POCl3, DMF
(94)
86%
CHO
N N
Me Me
When positions 1 and 2 are both blocked\ formylation can occur in the six!membered ring[ A
very elegant example of this is shown in Equation "84# where the Du} reaction proved to be the
method of choice for the regioselective formylation of ellipticine ð81S0110Ł[
OHC
N HMT, TFA
N (95)
N 97%
H N
H
HAl N N Me (2 equiv.)
CO2H CHO
2
(96)
75%
N N
The synthesis of formyl pyridines from oxidation of a methyl substituent has been achieved using
selenium dioxide "Equation "86## ð57CPB786\ 73CPB3803Ł or iodine:DMSO ð69JOC730Ł[ The most
popular method for oxidation of hydroxymethyl pyridines is by use of manganese dioxide\ for
example\ Equation "87# ð73JA529Ł[
O O O O
EtO EtO
OEt SeO2 OEt
(97)
N N 69% OHC N N
O O
MnO2, CH2Cl2
NH NH (98)
HO N 75% N
N OHC N
O But O But
i, BunLi OHC
ii, DMF
MeO NH MeO NH (100)
73%
N N
N i, MeLi N CHO
ii, DMF
O O (101)
52%
N N
i, Mg, EtMgBr
ii, DMF
(102)
O N Br 94% O N CHO
Heterocyclic Aryl Aldehydes 098
Many of the methods which have been used for the preparation of pyridine carboxaldehydes are
equally applicable to the synthesis of quinoline carboxaldehydes[ For example\ methyl quinolines
have been oxidised to the corresponding aldehydes using selenium dioxide ð30JA1543\ 65BSF678Ł\
quinoline esters have been reduced to aldehydes using dibal!H ð65BSF678Ł\ and certain quinolines
have been metallated and reacted with DMF or MFA to produce the formyl derivatives\ for
example\ Equation "092# ð63T3042Ł[
OMe OMe
i, BunLi
ii, MFA CHO
(103)
68%
N OMe N OMe
Scheme 7
In the case of thiazoles all three isomeric formyl derivatives have been produced using selective
lithiation procedures\ and quenching the resulting anions with a formamide ð76S887Ł[ Likewise\
formyl imidazoles may be made using analogous metallation reactions ð77TL2396\ 80JOC3185Ł[ Classi!
cal formylations of these heterocycles are di.cult\ and therefore not generally applicable[ Oxidative
methods appear to be applicable if the required starting materials are available[ For instance\ both
1!formylimidazoles and 1!formylthiazoles have been produced from selenium dioxide oxidation of
the corresponding alcohols ð55ACS1538Ł[
Copyright # 1995, Elsevier Ltd. All R ights Reserved Comprehensive Organic Functional Group Transformations
3.04
Ketones: Dialkyl Ketones
KEVIN E. B. PARKES
Roche Products Ltd., Welwyn Garden City, UK
and
STEWART K. RICHARDSON
University of Notre Dame, IN, USA
2[93[0 SATURATED UNSUBSTITUTED KETONES 001
2[93[0[0 From Alkanes 001
2[93[0[1 From Alkenes 002
2[93[0[2 From Alkynes 003
2[93[0[3 From Halides 003
2[93[0[4 From Alcohols and Their Derivatives 003
2[93[0[4[0 By oxidation of secondary alcohols 003
2[93[0[4[1 From diols 010
2[93[0[4[2 By oxidation of derivatives of alcohols 010
2[93[0[4[3 Rearran`ement of allylic alcohols 011
2[93[0[5 From Epoxides 011
2[93[0[6 From Acetals\ Enol Ethers and Enol Esters 012
2[93[0[7 From Aldehydes or Ketones 012
2[93[0[7[0 From saturated aldehydes or ketones 012
2[93[0[7[1 From unsaturated ketones 016
2[93[0[7[2 From a!functionalized ketones 017
2[93[0[8 From Carboxylic Acids and Their Derivatives 018
2[93[0[8[0 Reaction of carbon nucleophiles with acids and their derivatives 018
2[93[0[8[1 Other preparations from acids and acid derivatives 020
2[93[0[09 From Sulfur or Other Lower Chalco`en!containin` Precursors 020
2[93[0[00 From Nitro`en!containin` Precursors 021
2[93[0[00[0 From amines 021
2[93[0[00[1 From oximes\ hydrazones and their derivatives 022
2[93[0[00[2 From nitroalkanes 023
2[93[0[00[3 From nitriles 023
2[93[0[01 From Or`anosilanes 023
2[93[0[02 From Or`anoboranes 023
2[93[0[03 Methods Involvin` Umpolun` 024
2[93[0[03[0 Acyl anions and their equivalents 025
2[93[0[03[1 Other anion equivalents 026
2[93[1 BETA!UNSATURATED AND MORE REMOTELY UNSATURATED KETONES 027
2[93[1[0 Dialkyl Ketones with One Double Bond 027
2[93[1[0[0 From ketones 027
2[93[1[0[1 From carboxylic acid and carboxylic acid derivatives 039
2[93[1[0[2 Preparations involvin` rearran`ements 030
2[93[1[0[3 Miscellaneous preparations 031
2[93[1[1 Dialkyl Ketones with More Than One Double Bond 033
2[93[1[2 Dialkyl Ketones with Aryl or Heteroaryl Substituents 033
2[93[1[2[0 From ketones 033
2[93[1[2[1 From carboxylic acids and carboxylic acid derivatives 035
000
001 Dialkyl Ketones
2[93[1[2[2 Other preparations 035
2[93[1[3 Alkynyl!substituted Dialkyl Ketones 035
2[93[1[3[0 From ketones 035
2[93[1[3[1 Fra`mentation reactions 036
2[93[2 HALO!SUBSTITUTED DIALKYL KETONES "a!\ b! AND MORE REMOTE HALOGENS# 037
2[93[2[0 Introduction 037
2[93[2[1 Fluoroaliphatic Ketones 037
2[93[2[1[0 a!Fluoroaliphatic ketones 037
2[93[2[1[1 b!Fluoroaliphatic ketones 049
2[93[2[2 Chloroaliphatic Ketones 040
2[93[2[2[0 a!Chloroaliphatic ketones 040
2[93[2[2[1 b!Chloroaliphatic Ketones 042
2[93[2[3 Bromoaliphatic Ketones 042
2[93[2[3[0 a!Bromoaliphatic ketones 042
2[93[2[4 Iodoaliphatic Ketones 044
2[93[2[4[0 a!Iodoaliphatic ketones 044
2[93[2[4[1 b!Iodoaliphatic ketones 045
2[93[3 KETONES BEARING AN OXYGEN FUNCTION 045
2[93[3[0 OH!functionalized Ketones 045
2[93[3[0[0 a!OH!functionalized ketones 045
2[93[3[0[1 b!OH!functionalized ketones 048
2[93[3[0[2 g!Functionalized and more remotely OH!functionalized ketones 050
2[93[3[1 OR!functionalized Ketones 051
2[93[3[2 OX!functionalized Ketones 052
O
80%
(1)
O
O
Rh[(S)-BINAP]ClO4
(2)
87%, 99% ee
But
But
(S)-BINAP = (S)-2,2'-Bis(diphenylphosphine)-1,1'-binaphthyl
003 Dialkyl Ketones
2[93[0[2 From Alkynes
Mercury"II#!catalysed acid hydration of terminal alkynes is a well established method for the
synthesis of methyl ketones[ The transformation has also been reported using a gold"II# catalyst\
which has the advantage of requiring neutral conditions and can be performed on substrates
containing an alkene\ hydroxy or acetate functionality ð80JOC2618Ł[ Variants using mercury!impreg!
nated Na_on!H ð67S560Ł\ phenylmercuric hydroxide ð71JOC2220Ł\ or p!methoxybenzenetellurinic
anhydride have also been reported ð75TL5988Ł[
Alkynes may also be converted into ketones by hydroboration and oxidation of the intermediate
vinylborane[ Diborane and simple mono! and dialkylboranes give very poor regioselectivity in the
hydroboration^ however\ excellent results can be obtained either with dimesitylborane ð72TL0322Ł
or with thexyliodoboraneÐdimethylsul_de complex ð82TL4002Ł\ followed by a conventional basic
hydrogen peroxide workup "Equation "2##[
Prn O
Prn + (3)
Prn
O
1.0% 99.0%
The cobalt!catalysed combination of an alkene\ an alkyne and carbon monoxide is known as the
PausonÐKhand reaction\ and normally gives a cyclopentenone product[ However\ it has recently
been found that if the reaction is performed under nitrogen with the reagents adsorbed on silica in
the absence of solvent\ the saturated cyclopentanone is formed instead "Scheme 0# ð82TL1976Ł[
Co2(CO)6
AcN Co2(CO)8 ∆
AcN AcN O
76% 94%
Scheme 1
O O
Cr
O O
(1)
Peroxychromium species such as CrO4 = C4H4N ð66TL2638Ł\ and CrO6 ð75T608Ł and a number of
chromium"V# complexes ð79TL0472Ł have been used as reagents for secondary alcohol oxidation[
Although they do have advantages in some situations\ in particular in being neutral\ they have not
achieved widespread use[
"b# Man`anese rea`ents[ Simple manganate"VI# or manganate"VII# reagents are very powerful
and unselective oxidants with little application in organic synthesis\ although a variety of modi_ed
and more useful reagents are now available[ Probably the most important of these reagents for the
preparation of saturated ketones is copper manganate"VII# ð71JOC1689Ł\ which is generally used in
the form of a solid mixture of potassium manganate"VII# and copper sulfate ð68JOC2335Ł[ This
reagent appears to be a very mild as well as high!yielding oxidant and is compatible with functionality
as sensitive as an N!nitroso group "Equation "3## ð78SC104Ł\ although the reaction is inhibited by
remote unsaturation in the substrate ð72JA2077Ł[ Barium manganate"VII# has also been reported to
be an e}ective oxidant for secondary alcohols and a!hydroxyketones\ and has the advantage of not
only being more selective but also of having greater heat and light stability than earlier manga!
nate"VII#!based reagents[ Other potentially useful reagents include benzyltriethylammonium
manganate"VII# ð70AG"E#093Ł and solid potassium manganate"VII#\ which gives much improved
results under the in~uence of ultrasonic irradiation ð72CL268Ł[
OH NO O NO
N N (4)
92%
Less work has been done with manganate"VI# reagents^ however\ a mixture of potassium manga!
nate"VI#\ copper sulfate and alumina has been reported to selectively oxidize secondary and benzylic
alcohols in the presence of primary of allylic alcohols "Equation "4## ð78TL1448Ł[
OH OH O OH
(5)
65%
"c# Ruthenium rea`ents[ As with chromium and manganese reagents\ the challenge for chemists
wanting to develop oxidants of this class has been to moderate the reactivity and improve the
selectivity of simple ruthenium reagents[ In an interesting contrast to the other metal oxidants\
where modi_ed stoichiometric reagents have been developed\ the most successful approach towards
Saturated Unsubstituted 006
ruthenium!based oxidants has been the development of catalytic systems\ and three distinct systems
have been found to be useful[
Although not very widely used\ bis"triphenylphosphine#ruthenium"II# chloride appears to have
some potential as a catalytic oxidant of secondary alcohols[ It was _rst reported in combination
with N!methylmorpholine!N!oxide ð65TL1492Ł\ although more recent publications have used
bis"trimethylsilyl#peroxide ð77BCJ2596Ł\ or iodosylbenzene ð70TL1250Ł\ as cooxidant[
Rather more valuable are the oxidations in which the active species is ruthenium tetroxide[ These
are generally performed in a two!phase system with the substrate in an organic phase\ normally tri!
or tetrachloromethane\ and an aqueous cooxidant phase[ A careful study with octan!1!ol as substrate
and sodium bromate as cooxidant has de_ned the optimal conditions to be a pH of between 4 and
7 and a stirrer speed su.cient to break up the boundary between the phases ð77JOC0092Ł[ The
authors also emphasize that it is important to use the {hydrated| form of the oxide\ which actually
has a hydroxide structure\ since the anhydrous oxide is very insoluble and does not form the active
tetroxide under the reaction conditions[ Variants on this procedure use sodium bromate in a
phosphate bu}er with ruthenium trichloride as precursor of the tetroxide ð74TL1096Ł\ or use sodium
periodate ð76JOC0038Ł or hydrogen peroxide with didecyldimethylammonium bromide phase trans!
fer catalyst ð77JOC2442Ł as cooxidant[
Unquestionably the most important ruthenium oxidants\ and one of the most important recent
developments in oxidation methodology generally\ are the tetraalkylammonium perruthenates
developed by Gri.th and by Ley[ These use a catalytic tetraalkylammonium perruthenate\ generally
tetrapropylammonium perruthenate "TPAP#\ in the presence of 9[3 nm "3 A ý # molecular sieves with
N!methylmorpholine!N!oxide as regenerating oxidant to achieve the oxidation under very mild\
neutral conditions[ The reagent is notable for the wide range of functionality tolerated\ including
THP and silyl ethers\ alkenes\ epoxides and esters "Equation "5##\ and the fact that chiral centres a
to the newly formed carbonyl group are not epimerized ð76CC0514Ł[ The reagent has been the subject
of a review ð89MI 293!90Ł[
O O
(6)
73%
OH O
"d# Miscellaneous metal oxidants[ Despite their importance in epoxidation chemistry\ vanadyl
species have seen very little use in alcohol oxidation reactions\ although they are known to o}er a
high degree of selectivity for secondary over primary alcohols ð72TL4998Ł[
A wide range of molybdenum and tungsten salts can catalyse the oxidation of alcohols by
hydrogen peroxide or t!butyl hydroperoxide[ The research group of Ishii has been particularly active
in this area\ publishing a series of papers on a number of variants of which the tris"cetylpyridinium#
01!tungstophosphateÐhydrogen peroxide system appears to be optimal ð77JOC2476\ 77SC758Ł\
although Venturello et al[ recommend the related trioctylmethylammonium tungstophosphateÐ
hydrogen peroxide system ð80JOC4813Ł[ Benzyltrimethylammonium tetrabromooxomolybdate
"BnMe2N¦ MoOBr3−# ð73TL3306Ł\ and ammonium molybdate ð73TL062Ł\ are also known to catalyse
the hydrogen peroxide oxidation of alcohols[ Two molybdenum peroxy complexes\ "1# ð79TL3732Ł
and "2# ð76JOC4356Ł\ have also been reported as stoichiometric oxidants for alcohols\ although "2#
can also be used catalytically with hydrogen peroxide as cooxidant ð68JOC810Ł[
O
O O
Mo
Ph O O O
N O O
Mo O O
O O
Ph N
O
(2) (3)
A number of ferrates have been examined as potential oxidants for alcohols[ In one valuable
comparative study\ barium ferrate was found to show a very similar reactivity to barium manganate
007 Dialkyl Ketones
ð75SC612Ł[ Silver ferrate ð75SC100Ł\ and a mixture of potassium ferrate\ alumina\ and copper sulfate
ð75TL1764Ł\ have also been found to be potentially useful oxidants[
Iridium pentahydride catalyses the dehydrogenation of alcohols in a remarkable reaction that
requires no cooxidant or hydrogen acceptor but actually evolves gaseous hydrogen ð76TL2004Ł[
Raney nickel can also be used to dehydrogenate secondary alcohols\ although in this case 0!octene
is required as a hydrogen acceptor ð75JOC4371Ł[
A number of catalytic palladium systems for alcohol oxidation are known\ and the scope of the
method has been examined ð72JOC0175Ł[ The optimal conditions found employ 0Ð2 mol) of either
a palladium"9# or palladium"II# catalyst with bromobenzene as reoxidant[ The oxidation can also
be performed with tetrachloromethane or bromotrichloromethane as reoxidant ð74T4534Ł\ and
under phase transfer conditions with iodobenzene as reoxidant ð74TL5146Ł[
Copper"II# or zinc"II# nitrate supported on silica gel ð78JOC0420Ł\ and iron"III# nitrate supported
on clay ð79S738Ł\ have all been reported to oxidize secondary alcohols to ketones in good yield[
Primary and secondary benzylic alcohols are also oxidized\ although unactivated primary alcohols
are una}ected[ The complex of copper"II# bromide and lithium t!butoxide oxidizes secondary
alcohols in high yield ð81CL0074Ł[
Barton|s group have examined a range of pentavalent bismuth reagents for oxidizing secondary
alcohols and recommend triphenylbismuth carbonate ð68CC694Ł[ The reagent is of interest since
some normally sensitive functionalities\ such as pyrroles and indoles\ are una}ected[
Lanthanide reagents have received relatively little attention as potential oxidants for alcohols[
The most important exception is the cerium"IV#!catalysed oxidation of alcohols by sodium bromate
ð71TL428Ł\ which may also be performed with a polymer!supported catalyst using cerium"IV#
impregnated on Na_on resin ð78BCJ408Ł[ Ytterbium"III# nitrate is also known to catalyse the
oxidation of alcohols by iodosobenzene and has the unusual selectivity of oxidizing primary in
preference to secondary alcohols\ although good yields of ketones can be obtained with longer
reaction times ð82CL460Ł[
AcO OAc
F F
I OAc
I F
O
O
O
(4) (5)
O PhCHO
MgBr +
OMgBr 69% O
Scheme 2
Possibly related to the Oppenauer oxidation is the highly selective oxidation of secondary alcohols
on alumina using trichloroacetaldehyde as oxidant ð65TL2388Ł[ The method has been particularly
recommended for cyclobutanone preparations ð66S444Ł[
019 Dialkyl Ketones
–
+ AlMe2Cl
O+ HO
– AlMe2Cl
acrolein, AlMe2Cl
OAlMeCl O
acrolein
Scheme 3
O
N C3F7
C4F9
F
(6)
"i# Ethers
A wide range of alkyl and silyl ethers react with hydride!abstracting reagents to give an oxonium
ion which hydrolyses to a ketone on workup[ Thus methyl ethers of secondary alcohols are oxi!
datively cleaved by nitronium tetra~uoroborate ð66JOC2986Ł\ or uranium"VI# ~uoride ð67JA4285Ł\
and O!trimethylsilyl derivatives can be oxidized with trityl tetra~uoroborate ð65JOC0368Ł or with
nitrosonium tetra~uoroborate\ which will also oxidized stannyl ethers ð65S598Ł[ Sodium bromate\
in the presence of cerium"IV# ammonium nitrate ð79S786Ł or polymer!supported cerium"IV# or
chromium"III# catalysts ð78BCJ408Ł will oxidize a wide range of ether derivatives including methyl\
benzyl\ trimethylsilyl and t!butyldimethylsilyl\ with selectivity for secondary over primary deriva!
tives[ Alkyl ethers can be oxidized by copper"II# or zinc"II# nitrates suspended on silica ð78JOC2990Ł[
Silyl ethers can also be oxidized under rather milder conditions[ For example\ trimethylsilyl ethers
are oxidized using dimethyl sulfoxideÐoxalyl chloride\ although the conditions "−29>C for 29Ð34
min# are appreciably more vigorous than are normally required for alcohol oxidations
ð76JCS"P0#0110Ł[ t!Butyldimethylsilyl ethers are inert to the reaction conditions and hindered
trimethylsilyl ethers react appreciably less rapidly\ allowing some interesting selective oxidations to
be achieved "Equation "7##[ The Jones reagent will also oxidize trimethylsilyl ethers ð72S461Ł and\
in the presence of potassium ~uoride\ t!butyldimethylsilyl ethers to ketones in yields that compare
well with a conventional two!pot deprotectionÐoxidation sequence ð74SC648Ł[ t!Butyldiphenylsilyl
ethers are una}ected\ again allowing some interesting selective transformations to be achieved
"Equation "8##[ The oxidative deprotection and stability under alcohol oxidative conditions of silyl
ethers has been the subject of a very comprehensive review\ which includes extensive tabulations of
the reactivities observed ð82S00Ł[ Lastly in this section\ tributylstannyl ethers can be oxidized to
ketones by a combination of lithium bromide and copper"II# bromide ð81CL312Ł[
O O
TMS-O HO
(8)
74%
TMS-O O
(9)
TBDMS-O OSiPh2But 90% O OSiPh2But
TBDMS = t-butyldimethylsilyl
"ii# Esters
Ketones may be prepared under strictly neutral conditions by the photolysis of the pyruvate
esters of alcohols ð65JOC2929\ 65SC170Ł\ and the reaction has been applied to good e}ect in the
011 Dialkyl Ketones
preparation of a number of delicate carbohydrate ketones ð66JOC0105Ł[ Nitrite esters are oxidized
to ketones by dimethyl sulfoxide ð75T3022Ł\ and alcohols may be oxidized via their aci!nitro esters
ð68CC292\ 70TL1184Ł[ Both reactions can be regarded as variants of the Kornblum oxidation[
"iii# Carbonates
Treatment of alkyl allyl carbonates with palladium catalysts in the absence of phosphine ligands
gives good yields of ketones "Equation "09## ð73TL1680Ł[
O
O
O O
PdII
(10)
77%
HBr
(11)
O 93% O
H
OH O
H H H
LiBr, HMPA
+ (12)
O
R O R O R
(7) (9) (8)
HMPA = hexamethylphosphoramide
Saturated Unsubstituted 012
2[93[0[6 From Acetals\ Enol Ethers and Enol Esters
The chief importance of acetals in organic synthesis is as protecting groups for carbonyl
compounds[ As well as simple dialkylacetals\ 0\2!dioxanes\ and 0\2!dioxolanes\ many more complex
acetals have been used as protecting groups and allow the preparation and deprotection of ketones
under a remarkably wide range of conditions[ Readers interested in these aspects should refer to
one of the specialist works on protecting groups such as that by Greene and Wuts ðB!80MI 293!91Ł\
since the following discussion is only intended to highlight some of the more important approaches
to preparing ketones from simple acetals[
Traditional methods of ketone preparation from acetals are variants on the theme of acid!
catalysed hydrolysis\ and these have now been extended to use supported or heterogeneous acids
such as Amberlyst!04 ð73S0910Ł or wet silica gel ð67S52Ł\ which permit a much simpler reaction
workup[ However\ a more important objective of research in this area has been to develop less
strongly acidic conditions for acetal hydrolysis and to _nd methods that allow highly selective
deprotections to be performed[ One approach to the former goal is to use transacetalizations
which are catalysed by very mild reagents such as pyridinium tosylate ð68S613Ł\ and palladium"II#
bis"acetonitrile# dichloride ð74TL694Ł\ although hydrolyses with neutral reagents\ such as aqueous
DMSO ð78CL890Ł\ are also possible[ The use of aqueous DMSO is of particular note since it allows
dimethyl acetals to be hydrolysed in the presence of other\ more sensitive\ functionalities\ including
acetal!based alcohol protection such as methoxymethyl "MOM# or THP[ A number of procedures\
including silica!supported iron"III# chloride ð76S26Ł and samarium"III# chloride in the presence of
chlorotrimethylsilane ð78CL0512Ł\ allow acetals derived from ketones to be cleaved preferentially in
the presence of those derived from aldehydes[
A relatively recent discovery is the ability of a number of reagents to e}ect the {hydrolysis| of
acetals under strictly nonaqueous conditions[ These methods appear to involve an electrophilic
attack on one of the acetal oxygens leading to an oxonium ion which is cleaved to the ketone by
nucleophilic attack on the alkyl group[ The mechanism is illustrated in Scheme 3 for the case of
iodotrimethylsilane ð66TL3064Ł[ Other reagents which work in this way include diiododimethylsilane
ð89JOC1816Ł and phenyldichlorophosphate in the presence of sodium iodide ð75SC0246Ł[
I– I–
TMS-I O-TMS
O O + +O
O O
TMS
R1 R2
R1 R2 R1 R2
O
+ O-TMS
I
R1 R2
Scheme 4
Enol esters and silyl enol ethers are most often prepared from ketones as intermediates in other
reactions[ They are\ in general\ hydrolytically labile compounds\ making their transformation back
to ketones relatively straightforward should it be required[ Tributyltin ~uoride with palladium
catalysis has been recommended for the hydrolysis of more stable silyl enol ethers ð72JA4692Ł[
E+
M
S
L
(10)
Several important methods of ketone alkylation involve nitrogen derivatives of the ketone\ of
which the _rst to be introduced were enamines ð43JA1918Ł\ followed by metallated imines ð52JA1067Ł\
and lastly metallated hydrazones ð65TL2Ł[ The alkylation of ketones via their nitrogen derivatives
has been the subject of a Synthesis review ð72S406Ł[ One particularly important application of
these methods is for the enantioselective alkylation of ketones ð70JA2970\ 68CPB1659\ B!72MI 293!90Ł[
Probably the best established of these methods is that developed by Enders\ which employs hydra!
zones derived from "S#!"−#! or "R#!"¦#!0!amino!1!methoxymethylpyrrolidine "abbreviated to
SAMP and RAMP\ respectively# and gives reliably high enantioselectivities of predictable sense
"Scheme 4# ðB!73MI 293!91Ł[
Some stable enolate species\ such as silyl enol ethers\ will react with alkylating agents and\ after
workup\ allow the isolation of good yields of alkylated ketones[ In the case of silyl enol ethers the
reaction is Lewis acid!catalysed and involves the electrophilic attack of a carbocation on the enol
ether[ This mechanistic pathway also rationalizes the major limitation of the method\ which is
restricted to tertiary alkylating agents and is thus complementary to metal enolate methods which
do not allow alkylations with tertiary halides[ The other major advantage of the method is that
it allows one to harness the well!developed techniques for preparing either the kinetic or the
thermodynamic silyl enol ether with high speci_city to be used to control the regioselectivity of the
alkylation[ Early work in the area has been reviewed ð71AG"E#85Ł[ Further research has been directed
to trying to extend the bene_ts of this good regiocontrol to a wider variety of alkylating agents[
One approach has been to use an a!phenylthio halide to introduce an a!phenylthio alkyl group from
which the phenylthio substituent is removed in a subsequent reduction "Scheme 5# ð77T3196Ł[
Silver"I# tri~uoroacetate has been found to activate primary alkyl halides to nucleophilic attack by
silyl enol ethers\ although primary alkyl bromides and secondary alkyl iodides are unreactive
ð81TL0744Ł[ Lastly\ intramolecular alkylations are an important route to cyclohexanones and cyclo!
heptanones ð67JOC699Ł\ but not cyclopentanones\ in accord with Baldwin|s rules ð66CC122Ł[
Saturated Unsubstituted 014
O
i–iv
N
N OMe 70%
SAMP
O 87% >95% ee
RAMP
87% O
i–iv
N
N OMe 70%
>95% ee
Scheme 5
O-TMS i, TiCl4 O O
ii, PhSCH2Cl Raney Ni
SPh
87% 99%
LDA, TMS-Cl
O 97%
Et3N, TMS-Cl
83%
O-TMS i, TiCl4 O O
ii, PhSCH2Cl Raney Ni
PhS
71% 98%
Scheme 6
"ii# Homologation
Although any preparation of functionalized ketones involving carbon!to!carbon bond formation
and starting from a ketone can be thought of as a homologation\ this section will deal only with
those reactions which increase the number of carbon atoms without any increase in the functional
complexity of the molecule[ Homologations of this sort\ particularly by one carbon atom\ have
proved particularly important for the synthesis of medium!ring ketones by the ring expansion of
more accessible\ normal ring ketones[
One important and well established reagent for ketone homologation is diazomethane
ð43OR"7#253Ł\ although trimethylsilyldiazomethane has been recommended as a safer alternative
ð71CPB008\ 71CPB2279Ł[ Epoxide formation can be a signi_cant\ or even dominant\ side reaction
although good results are generally obtained with cyclic ketones[ One alternative which does
not appear to share this drawback is dibromomethyllithium\ which adds to a ketone to give a
dibromomethylcarbinol[ This rearranges to the homologated ketone on further treatment with
butyllithium in a reaction which is proposed to proceed by a carbenoid mechanism and which allows
the regioselective homologation of unsymmetrical ketones "Scheme 6# ð66BCJ0481Ł[ The reaction of
a ketone with phenylselenoalkyllithium gives a hydroxyselenide which may also be rearranged to
the homologated ketone "Scheme 7# ð89BSF570Ł[ Both the selenium and dibromomethyllithium
chemistry have been extended to allow the introduction of an RCH unit ð68S857Ł[
Dowd et al[ have developed a very versatile\ free!radical!mediated ring expansion of b!keto esters[
015 Dialkyl Ketones
Br O
O
Br OH
LiCHBr2 BunLi
78% 79%
Scheme 7
PhSe O
O
HO AgBF4
+ SePh
70% 85%
Li
Scheme 8
The method allows homologation by one ð80TL454Ł\ three or four carbons "Equation "02## ð78T66Ł\
and appears to be quite tolerant of other functionality[
O
O O
CO2Et Bu3SnH, AIBN CO2Et
+ (13)
I
CO2Et
71% 25%
AIBN = 2,2'-azobisisobutyronitrile
"iii# Transposition
0\1!Carbonyl transpositions regularly prove to be valuable in organic synthesis and\ fortunately\
are the subject of a very comprehensive review ð72T234Ł[ Three chief groups of methods\ involving
sulfur\ silicon or boron chemistry\ can be distinguished\ all of which have variants allowing for the
introduction of an alkyl group at the original ketonic carbon[
The sulfur methods generally involve the preparation of an a!thioketone\ which is subsequently
converted into a vinyl sul_de and hydrolysed to give the transposed ketone "Scheme 8# ð68TL420Ł[
Transpositions during which an additional alkyl group is introduced are also possible ð73BCJ097Ł[
The boron!based transpositions involve the addition of a Grignard reagent to the ketone and
dehydration of the resulting carbinol to give an alkene which is then hydroborated and oxidized to
give the transposed\ alkylated ketone "Scheme 09# ð50JA1840Ł[
The silicon!based methods involve the initial preparation of a vinylsilane followed by transposition
via an a!silyl epoxide "Scheme 00# ð79JOC2917Ł[
O NHTs NHTs
N N
TsNHNH2 i, BunLi, TMEDA BunLi
SMe
ii, MeSSMe
SMe O
HgCl2, MeCN, H2O
Scheme 9
Saturated Unsubstituted 016
O R OH R R
RMgX –H2O i, B2H6 O
ii, chromic acid
Scheme 10
iii, TMS-Cl
TMS
O
OH chromic acid
Scheme 11
O O
i, Fe2(CO)4
O ii, Zn/Cu
Br Br + (14)
63% O
Br Br
Hydroxide is a relatively poor leaving group and consequently many of the single!electron
reductants that are very e}ective for a!dehalogenation work poorly on a!hydroxyketones[ It is
therefore often preferable to activate the acyloin _rst\ by acylation or sulfonation\ and then reduce
with samarium"II# iodide ð75JOC0024Ł or the vanadium"II#ÐTHF complex ðV1Cl2"THF#5ŁðZn1Cl5Ł
ð81CL0784Ł[ However\ a!hydroxyketones can be reduced directly with lithium diphenylphosphide\
which presumably adds 0\1! to the ketone and then undergoes a Wittig type reaction ð75JOC1267Ł\
and with trimethylsilyl iodide ð68SC554Ł\ in which it is most likely the a!trimethylsilyloxy derivative
which undergoes the reduction[
Relatively few alternatives to the standard reductive desulfonation of a!sulfonylketones with
aluminum amalgam are available ð53JA0528Ł[ However\ the reduction can be achieved with sam!
arium"II# iodide ð75JOC0024Ł and photochemically in the presence of a rhodium"II# sensitizer and a
Hantzch ester as ultimate reducing agent ð75CL76Ł[
a!Diazoketones are very versatile intermediates from which a wide range of derivatives may be
prepared[ The two most important reactions from the point of view of this chapter are cyclo!
propanation and the intramolecular insertion into C0H bonds\ generally to give cyclopentanones[
Both processes are mediated by copper"II# and rhodium"II# catalysts and have been the subject of
a review ð80T0654Ł[ The insertion reaction can occasionally provide a very elegant cyclopentanone
ring synthesis\ the major drawback being the poor regiospeci_city[ Several strategies for improving
the selectivity are known\ including suitable placement of electron!withdrawing groups\ such as
esters\ which protect C0H bonds a and b to them from attack ð77TL1172Ł\ using rhodium catalysts
with bulky ligands to favour methylene insertion over methine insertion ð81TL1698Ł\ or placing
double bonds to harness the preference for allylic over nonallylic insertion ð80T6392Ł[ Enantio!
selective versions of the reaction are also known ð72JA4824Ł[
i, Zn/Cu, ultrasound
NH-t-BOC ii, PdII, AcOCH2COCl NH-t-BOC
I AcO (15)
CO2Me 64% O CO2Me
t-BOC = t-butoxycarbonyl
As well as the zinc!derived cuprates\ a wide range of other organocopper species have been used
to prepare ketones from acid chlorides[ When an unfunctionalized primary alkyl group is to be
coupled\ simple lower!order cuprates work well and are compatible with acid chlorides containing
ester\ nitrile and iodo groups ð61JA4095Ł\ although for more hindered cases higher!order cuprates
give better results ð77OSC"5#137Ł[ It is even possible to prepare suitable organocopper species direct
from the alkyl halides containing ester\ nitrile and chloro groups by reaction with the copper"9#
complex obtained by treating lithium 1!thienyl cyanocuprate with lithium naphthalenide ð78SC0722Ł[
The acylation of organomanganese halides\ which are prepared from a Grignard or alkyllithium
reagent and manganese"II# halide\ has been the subject of a detailed study ð73T572Ł[ Organo!
manganese couplings can also be performed catalytically by adding a Grignard reagent to a solution
of the acid halide and 2 mol) of MnCl3Li1 ð81TL3328Ł[ Other reagents that\ although less widely
used or studied\ appear to have considerable potential for preparing ketones from acid chlorides
include organothallium ð89JOC2257Ł\ and organovanadium ð75TL818Ł reagents[
Although many of the methods described above for preparing ketones from acid halides also
work with acid anhydrides\ the reaction is somewhat limited by the fact that only half of the acid is
incorporated into the product[ This drawback can be avoided if mixed anhydrides are used and the
idea has been shown to be practical for both Grignard reagents ð67SC48Ł\ and organomanganese
reagents ð68SC528Ł\ although few applications have been reported[
The preparation of a ketone by the reaction of a simple ester with an organometallic reagent
appears to be a particularly di.cult transformation which is only successful if special precautions
are taken to prevent further reaction of the ketone product[ This can be achieved by performing the
reaction with an alkyllithium reagent at low temperature "−009>C# in the presence of chloro!
trimethylsilane\ which presumably traps the tetrahedral intermediate ð75JOC840Ł\ or with a Grignard
reagent in the presence of triethylamine ð79S766Ł or lithium diisopropylamide ð76HCA0634Ł\ which
protects the ketone by enolization[ The introduction of a bulky silyl substituent at the a position of
the ester also very e}ectively prevents the reaction proceeding beyond the ketone stage ð74JOC4159Ł\
and cyclic ketones can be prepared in high yields by the samarium"II# iodide!mediated cyclization
of v!iodo esters\ a reaction which appears to involve the addition of an alkylsamarium nucleophile
to the ester "Equation "05## ð82JOC6105Ł[
MeO2C
I SmI2, THF
O (16)
93%
A number of ketone preparations from activated esters have been reported which\ despite the
requirement to prepare the particular ester\ do appear to have some advantages[ For example\ both
selenoesters ð72TL3244Ł and 1!pyridyl esters ð72JOC1597Ł react with organocuprates to give high
Saturated Unsubstituted 020
yields of ketones[ The latter reaction has the distinct advantage over the analogous reaction of an
acid chloride with a dialkylcuprate of using both alkyl groups from the organometallic reagent[
Perhaps surprisingly\ tertiary amides can be converted directly into ketones by reaction with an
alkyllanthanum tri~ate ð76TL3280Ł[ However\ most ketone preparations from amides use particularly
reactive derivatives\ such as acyl imidazoles ð89SC1572Ł\ or acyl aziridines ð73TL700Ł\ and N!methoxy!
N!methyl "Weinreb# amides[ The latter\ in which internal chelation stabilizes the tetrahedral inter!
mediate and prevents overreaction\ are rapidly becoming one of the preferred acid derivatives for
ketone preparation[ The idea has been generalized to N\N?!dimethoxy!N\N?!dimethylurea\ which
has been found to react with a wide range of organometallic reagents to give N!methoxy!N!methyl
amides\ which can then be coupled with a second organometallic reagent to give an unsymmetrical
ketone ð80JOC1800Ł[
The preparation of ketones by the reaction of Grignard reagents with nitriles has a long history\
although the conditions are quite critical\ with aromatic solvents being required for good results
ð79TL044Ł[ The reaction is also catalysed by the addition of copper"I# salts\ which allow the reaction
to be used for the preparation of quite hindered ketones ð76JOC2890Ł[
The reaction of a carboxylic acid with two equivalents of an alkyllithium reagent is a well
established preparation of ketones which works because the dianionic tetrahedral intermediate does
not break down under the reaction conditions to liberate the ketone\ which is therefore unavailable
for overreaction to the tertiary alcohol[ In practice\ obtaining good yields of ketone\ free from
carbinol\ depends heavily on good experimental technique\ both in the addition of the alkyllithium
and in the hydrolysis of the tetrahedral intermediate ð69OR"07#0Ł[ Improved workups in which the
reaction is quenched with aniline ð70JOC2817Ł\ gaseous formaldehyde ð70JOC2817Ł or\ for the speci_c
case of methyl ketone preparation\ with chlorotrimethylsilane ð72JOC0449Ł have been described\ and
the addition of cerium"III# chloride to the reaction mixture has been found to be highly bene_cial
ð83TL192Ł[ It is also possible to generate the lithium salt of the carboxylic acid from an alkyllithium
and carbon dioxide and react it in situ with a second equivalent of a di}erent alkyllithium to give
an unsymmetrical ketone ð81AG"E#0924Ł[
Et
N+
Cl BF4–
O
(12)
SR3 –R3S–
SR3
R1
R2
+ O
SR3 H2O
R1 R1
R2 R2
SR3 +H+
R1
R2
Scheme 12
+
Me N H3O+
O
N 91%
dbu = 1,5-diazabicyclo[5.4.0]undec-5-ene
Scheme 13
OLi
TMS O
HN TMS O N
i, BunLi N
OH O
N
SiO2, H2O
87%
Scheme 14
BH2
i, trans-2-butene MeCHO
B
ii, 1-pentene
i, Cl2CHOMe, ButOLi
ii, H2O2, HO–
B
EtO 66%, 70% ee O
Scheme 15
O
Jones
n-C8H17
51%
PhMe2Si n-C8H17
OH
Scheme 16
Bun
n-C6H13 Bun
H2O2, HO– O
B SnBu3 62% n-C6H13 n-C5H11
Scheme 17
–
Br i, BunLi Bu3B O
i, EtOSO2F
Et
MeO OMe ii, Bu3B MeO OMe ii, H3O+ Bu
Scheme 18
O O
Bu3SnH, AIBN
O (17)
SePh 70%
O O
AIBN = 2,2'-azobisisobutyronitrile
Many d0 synthons that have been described and can be classi_ed either as formyl dianion
equivalents\ in which the two carbonyl substituents are introduced in successive alkylating steps\ or
as acyl anion equivalents\ in which one of these substituents is already present[ A compilation of
acyl anion equivalents reported up to the early 0879s is available and includes details of the
electrophiles used ð71MI 293!90Ł[ The general topic of nucleophilic acylation has been the subject of
a review ð65T0832Ł\ as has the chemistry of silicon!containing carbonyl equivalents ð71CSR382Ł[
Saturated Unsubstituted 026
It should also be noted that many of the formyl anion equivalents discussed in Chapter 2[90[0[03[0
can be doubly alkylated and are thus also formyl dianion equivalents[
A large proportion of formyl anion and dianion equivalents are based on sulfur[ This group
includes one of the earliest and still one of the most important synthons\ 1!lithio!0\2!dithiane\
which has been the subject of several reviews ð66S246\ 78T6532Ł[ Formyl anion synthons containing
sulfur"VI#\ such as "02# ð73CC375Ł\ are also known[
–
PhSO2 TMS
(13)
d0!Formyl anion and dianion synthons based on nucleophilic metal carbonyl derivatives can be
very useful reagents for ketone synthesis[ The best!known example is the Collman reagent\
Na1Fe"CO#3\ which reacts with primary and secondary halides and sulfonates to give an alkyl iron
complex which can be alkylated a second time to liberate the required ketone "Equation "07##[ The
reagent tolerates ketone\ ester or nitrile functionality\ but has the drawback of being somewhat
basic\ causing elimination of some substrates\ in particular of tertiary halides and sulfonates\ and
being restricted to quite reactive alkylating agents "generally primary iodides# in the second step
ð64ACR231Ł[ A number of related ionic iron carbonyl complexes ð68CL210\ 78BCJ1617Ł have also been
used[
i, Na2Fe(CO)4
ii, EtI CO2Et
Br
CO2Et (18)
74% O
Acyl anion equivalents\ which already contain one of the carbonyl substituents\ are also important
ketone precursors[ Two principal groups can be identi_ed] those based on vinyl anions\ and those
using protected cyanohydrins or related species[ The latter\ which are extensions of the benzoin
condensation\ have been the subject of a review ð72T2196Ł[ One particularly important class of these
synthons is the dialkylaminonitriles which\ since they are prepared by the Strecker reaction of an
aldehyde\ allow a fairly direct preparation of ketones from aldehydes[ Lastly\ a wide variety of
metallated vinyl compounds have been prepared and used as acyl anion equivalents[ Examples
include lithium and Grignard derivatives of vinyl silanes ð71CSR382Ł\ and lithiated derivatives
of vinyl sul_des ð73BCJ0752Ł\ vinyl esters ð70T2886Ł\ vinyl carbamates ð89JOC4579Ł and enamines
ð70CC0010Ł[
O
HO
MnIII, Bu3SnH H
(19)
75%
H
027 Dialkyl Ketones
Lastly\ a number of a1 synthons are known\ although they have most often been reported reacting
with fairly stabilized anions such as enolates or keto esters[ However\ the sulfur!substituted allyl
acetate "03# will couple with a lithium dialkylcuprate and thus acts as an a!keto cation equivalent
"Scheme 08# ð68JA3302Ł[
SPh SPh O
Bu2CuLi HgCl2
OAc Bun Bun
89%
(14)
Scheme 19
CO O
CO O O
O Fe ∆ ∆
52% 38% Fe
CO
CO
Scheme 20
b! and More Remotely Unsaturated 028
O-TMS i, HgCl2 O
ii, HCl
(20)
83%
O(1/2Zn) O OH O
PhSeCH2CHO MsCl, Et3N
95% 82%
SePh
Scheme 21
O
Pd0 O
O (21)
96%
O
O
O
O H
N Pd0
H (22)
47%, 100% ee
Allyl halides\ because of their high SN0 reactivity\ are e}ective electrophiles in the Lewis acid!
catalysed alkylation of silyl enol ethers ð68TL0408\ 68TL3860Ł[ The reaction is discussed in more detail
in Section 2[93[0[7[0[
039 Dialkyl Ketones
"iii# Conju`ate addition of unsaturated nucleophiles to a\b!unsaturated ketones
Although the methodology used for the conjugate addition of carbon nucleophiles is broadly
similar\ irrespective of whether or not the nucleophile contains carbonÐcarbon double bonds\ the
rather di}erent character and generation of vinyl! and allylmetal reagents justi_es some additional
discussion beyond that of Section 2[93[0[7[1[
Hydrometallation of alkynes is an attractive way of preparing alkenylmetal reagents[ For example\
hydroalumination of an alkyne gives an alkenylaluminum reagent which can either be used as a
precursor of a cuprate ð89JOC0314Ł or treated with methyllithium to form an ate complex which will
add 0\3! to an enone ð68JOC0327Ł[ Alkenylzirconium reagents\ prepared analogously by hydro!
zirconation of an alkyne\ can also be used as cuprate precursors ð89JA6339\ 89JA6330Ł or alternatively
can be activated towards conjugate addition\ even to hindered enones\ by Ni"acac#1\ or Ni"acac#1
prereduced with dibal!H ð79JA0222Ł[ Alkenylboranes\ prepared by the reaction of an alkyne with 8!
borabicycloð2[2[0Łnonane "8!BBN!H#\ also undergo e.cient conjugate addition to acyclic enones
ð65JA6721Ł[
Allylsilanes add 0\3 to enones in the presence of titanium"IV# chloride ð66JA0562Ł\ or trityl
perchlorate ð76CL178Ł catalysts[ Impressively\ the reaction is equally successful with b\b!dis!
ubstituted enones "Equation "12##\ and the resulting enolate intermediate can be trapped with
carbon electrophiles ð68CL134Ł[ Allylstannanes undergo 0\3!addition to enones in the presence of
trimethylsilyl tri~ate\ to give the product in which the allylstannane has coupled at its more hindered
position "Equation "13## ð80SC14Ł[ Allylsilanes do not react under these conditions and the reaction
fails for b\b!disubstituted enones[ The reaction can also be performed photochemically^ under these
conditions couplings with b\b!disubstituted enones are successful\ although products from both a!
and g!attack are also seen ð80CL0902Ł[
TiCl4
+ TMS (23)
85% O
O
O O-TBDMS
TBDMS-OTf
+ Bu3Sn (24)
88%
O
TMS PriCOCl, AlCl3
(25)
75%
b! and More Remotely Unsaturated 030
2[93[1[0[2 Preparations involving rearrangements
O
i, NaH
Cl O i, NaH (2 equiv.) OH ii, 200–215 °C O
+ O
OH OH ii, H3O+ 78%
Scheme 22
O-TMS O
O
TMS-Cl, Et3N O HIO4
O
84% 72%
Scheme 23
O OMgCl
MgCl O MgCl
Cl Cl 70 °C
OH O
200 °C
Scheme 24
R OH O
Et3Al
(27)
MsO H H R
Cl
• O Cl
Cl Cl NaOMe dibal-H
CO2Me
75% 83%
O OMe
OH i, MsCl, pyridine
ii, HClO4
63%
OMe O
Scheme 25
O OH BF3•Et2O O
TMS
But 77% But
Scheme 26
O O
+
Bun Bun
5:1
HMPA = hexamethylphosphoramide
Scheme 27
i, AlCl3
NO2 ii, TiCl3
TMS n-C10H21
+ O (28)
74% n-C10H21
O
AgF
Cl + (29)
TMS-O
53%
The free!radical fragmentation of b!trialkylstannyl alkoxy radicals has been employed in several
preparations of remotely unsaturated ketones[ In the most direct approach\ the alkoxy radical is
generated by treatment of the corresponding alcohol with lead"IV# acetate ð73TL4224Ł or with
iodosobenzene boron tri~uoride etherate and dicyclohexylcarbodiimide ð73CC0996Ł and gives a
product whose double!bond geometry is determined by the stereochemistry of the starting material[
Alternatively\ the required oxygen radical can be produced by the intramolecular addition to a
ketone of an alkyl radical generated by tin hydride reduction of a halide\ providing a ~exible and
elegant ring expansion methodology "Equation "29## ð77CC0393Ł[ Similar products have also been
prepared via the Wharton fragmentation of monosulfonates of 0\2!diols ð74JOC064Ł[
O
O
SePh Bu3SnH (cat.), AIBN
(30)
89%
SnBu3
AIBN = 2,2'-azobisisobutyronitrile
033 Dialkyl Ketones
2[93[1[1 Dialkyl Ketones with More Than One Double Bond
Ketones containing more than one nonconjugated double bond are generally prepared by methods
that are directly analogous to those used for the preparation of saturated ketones "Section 2[93[0#
or ketones with a single nonconjugated double bond "Section 2[93[1[0#[
The oxy!Cope rearrangement\ a powerful approach to d\o!unsaturated ketones "Section
2[93[1[0[1#\ has been extended by several workers to give multiply unsaturated ketones[ For example\
2\4!hexadienones can be prepared by replacing one of the double bonds in the 0\4!hexadiene unit
with an alkyne "Equation "20## ð73S0909Ł or an allene "Equation "21## ð82JOC4371Ł[ In both cases
the rearrangement products contain additional b\g unsaturation but di}er in placing the double
bond endo or exo to the ring[ The acetylenic rearrangement is also catalysed by silver"I# salts
ð75T0222Ł[
CO2Et CO2Et
NaH
(31)
45%
OH O
CO2Et CO2Et
NaOEt
(32)
• 80%
OH O
Wender|s group has developed a double oxy!Cope rearrangement which allows the preparation
of triply unsaturated cyclic ketones\ which are ring!expanded by eight carbon atoms[ One of the
challenges of this chemistry has been the preparation of the a!butadienyl ketone precursors required\
and several approaches which are of general interest for unsaturated ketone preparation have been
developed "Scheme 17# ð70T2856\ 70TL1360\ 73CC423Ł[
i, MeS SMe
Li i, Ph3P=CH2
ii, Ac2O OAc ii, LAH
iii, HgCl2 iii, CrO3•pyridine
O
73% O 64%
O OH O
Li KH
70% 90%
Scheme 28
MeO
MeO O-TBDMS
hν
(33)
74% MeO
MeO
O
Br
O
O Ph2CuLi
(34)
81%
Ph
Br
N N
N
S N
Ph
(15)
O O
O O AcO
+ (35)
65%
OAc
OAc
O
Ph
Scheme 29
Although pinacol rearrangements are generally of rather limited synthetic utility\ the high
migratory aptitude of aryl substituents allows the regio! and stereospeci_c rearrangement of chiral
vic!diol monosulfonates to a!aryl ketones of high optical purity "Equation "16## ð72TL3886Ł[
O
TsNHNH2 O
(37)
O 80%
Ph
Ph
O
N N
H2N Ph N Ph 110 °C
O
O 68%
O
Scheme 30
HO Bun O
NaH
Bun (38)
84%
SeO2Ph
037 Dialkyl Ketones
2[93[2 HALO!SUBSTITUTED DIALKYL KETONES "a!\ b! AND MORE REMOTE
HALOGENS#
2[93[2[0 Introduction
Although there is a considerable body of information on haloketones scattered throughout the
literature\ few attempts have been made to gather and collate the data[ One notable exception to
this is a _ne chapter by DeKimpe and Verhe on the synthesis and chemistry of a!haloketones in one
of the Updates from the Chemistry of the Functional Groups monographs edited by Patai and
Rappoport ðB!77MI 293!90Ł[
O O
Cl AgBF4
(39)
F 90%
F F
O O
O O
F3C
Bu4NF F
TMS (40)
70%
O-TMS O
TMS-O + O
N
–OTf
F
(41)
51%
F
TMS-O O
H H
F
+
N
(BF4–)2
+
N
Cl
(16)
Cl
F3CSO2
N F N F Cl
F3CSO2 S
O N
O S F
O
O
(17) (18) (19)
O– Na+ O
(–)-(19)
(42)
F
40%, 75% ee
049 Dialkyl Ketones
"v# From acids or esters
The preparation of more highly ~uorinated ketones is often approached by the assembly of
appropriately ~uorinated building blocks using carbon!to!carbon bond forming reactions[ For
example\ the reaction of ethyl tri~uoroacetate with Grignard reagents ð76JOC4915Ł\ of ethyl
per~uoroalkanoates with phosphorus ylides ð81JOC2796Ł\ and of esters with per~uoroalkyllithium
reagents ð76CL0042Ł have all been used to prepare alkyl per~uoroalkyl ketones[ Ketenes derived
from primary\ but not secondary\ acid chlorides can be trapped with tri~uoroacetic anhydride to
give tri~uoromethyl ketones after hydrolysis and decarboxylation "Equation "32## ð81TL0174Ł[
O O
Cl CF3
i, pyridine
AcO AcO
ii, TFAA
(43)
67%
F i, NaI
i, LDA ii, Raney Ni
S F ii, Me2CH(CH2)2Br
S 69%
O O O O
:
Scheme 31
O NEt2
F
Li
F
(20)
+
S
–OTf
CF3
(21)
O
Oxone, HCl
Cl
n-C6H13 n-C6H13 (44)
71%
Cl
Ph Ph
O OH O O
H chromic acid H
N N (46)
N CCl3 83% N CCl3
H H
O O
O ClCH2Li O
Cl (47)
C6H13 OEt 62% C6H13
i, BrClCHLi
ii, (Bun)2CuLi O
O iii, H3O+ Bun
Prn (48)
Prn OEt 87%
Cl
Trichloromethyl ketones have been prepared both by the reaction of trichloroacetyl chloride
Halo!substituted 042
with organozinc reagents\ and by the addition of trichloromethyl anions\ generated by the facile
decarboxylation of sodium trichloroacetate\ to aldehydes\ followed by oxidation of the resulting
alcohols with chromic acid ð81TL2324Ł[
O O O O
i, LDA, n-C9H19CHO EtMgBr
S Prn S Prn
Ph Ph n-C9H19 n-C9H19
ii, Swern oxidation
X X Prn X
X = Cl, Br
Scheme 32
O pyridine•HCl O
(49)
70%
Cl
Br O
NBS (aq.)
Br (50)
85%
O O
O
Br O
Br O
O
(22)
Br
O Li O
Br Br
OEt (51)
67%
Cl Cl Br
O
O DMSO, BF3•Et2O, NaI
(52)
75%
NO2 I
O O
O can, I2, MeOH
+ (53)
83%
I I
96 : 4
can = ceric ammonium nitrate
045 Dialkyl Ketones
2[93[2[4[1 b!Iodoaliphatic ketones
Relatively little literature is available on the preparation of b!iodo ketones\ although they can be
prepared by the conjugate addition of iodotrimethylsilane to enones\ followed by hydrolysis of the
intermediate enol silane ð68JOC0327Ł[
R
O O
R33SiO R1 Ph R
N
R4 R2 PhSO2
S N
O
O
(23) (24) (25)
Bearin` An Oxy`en 046
OSiR3 O
HO
mcpba OSiR3
(54)
72%
Hydroxymethyl anion equivalents "e[g[\ "15## will attack acids or their derivatives to give
a!hydroxy ketones ð68JOC3506\ 76TL0736Ł[ A complementary approach involves attack by
organometallic reagents at O!TMS cyanohydrins ð72TL3964\ 75TL0822Ł\ and many examples of this
transformation have appeared in the literature[
Li O
TMS O OLi
(26)
The development and use of acyl anion equivalents ðB!76MI 293!90\ 80COS"0#494Ł\ including
0\2!dithiane ð78T6532Ł\ has been one of the more important advances in organic chemistry in the last
two decades[ Ogura|s research group has reported extensively on the use of acyl anions in which
the anion is stabilized by sulfur in a higher oxidation state "e[g[\ "16##[ These acyl anions have been
used for the preparation of a!hydroxy carbonyls ð75TL2554\ 80COS"0#494Ł[ The anion "17# has been
shown to react with aldehydes or ketones to give a!hydroxy methyl or a!hydroxy methyl!a?!hydroxy
ketones depending on the reaction conditions ð78H"17#410Ł[ Heteroatom substituted alkenyl anions like
"17# are\ in fact\ well recognized acyl anion equivalents and readily attack aldehydes and ketones[
SMe O OCONEt2
Li
SO2Ar O Li Li
(27) (28) (29)
Other variations "e[g[\ "18## also give oxygenated ketones ð63JA6014\ 89JOC4579\ 80T2642Ł[ Knochel
and co!workers have recently disclosed the use of alkenyl boronate esters as acyl anion equivalents
"Scheme 22#[ The organozinc reagents add to a number of electrophiles\ including aldehydes\ to
give multifunctional ketones ð81TL2606Ł[ Cyanohydrins are also well!known acyl anion equivalents\
and their use has been reviewed ð80COS"0#430Ł[ The use of thiazoles and also thiazolium salts for the
preparation of hydroxy aldehydes "Chapter 2[90[3[0# has also been applied to
a!hydroxy ketones[ The anion of 2!methylbenzothiazolium bromide reacts chemoselectively\ _rst with
aldehydes and then paraformaldehyde to give the expected product "Scheme 23# ð74JOC592Ł[ The
adduct between an aldehyde or ketone and 1!lithiobenzothiazole can be further elaborated via
alkylation\ attack by organometallics and hydrolysis "cf[\ Scheme 18 in Chapter 2[90[3[0[0#
ð77BCJ2526Ł[
i, RCHO, BF3•Et2O O
O i, Zn, THF O ii, H2O2
Prn R
B B
Prn O ii, CuCN•2LiCl Prn O 75–87%
OH
I Cu(CN)ZnI
Scheme 33
S S R
base, RCHO, CH2O O– O
N+ N+ OH OH
R
Me Me
Scheme 34
A series of papers from Katritzky|s group has demonstrated the use of benzotriazoles for the
preparation of a variety of functional groups[ In one of these publications\ the authors disclose the
use of the anion derived from "29# as an acyl anion\ and describe its capture by aldehydes[ Subsequent
047 Dialkyl Ketones
hydrolysis gives hydroxy ketones ð80JOC5806Ł[ This paper also gives an extensive list of references
to other acyl anions[ A method for the hydroxyalkylation of acyl anions under mild\ nonbasic
conditions has been reported[ Alkyl halides add to aryl isocyanides in the presence of samarium"II#
to give a metalloimine which can add to ketones "Scheme 24#[ A number of acid! and base!sensitive
groups are compatible with the reaction conditions^ thus\ the method can be used to prepare highly
functionalized a!hydroxy ketones ð82JOC0347Ł[ The direct metallation of aldehydes to acyllithium
reagents can be achieved in only a few speci_c cases\ in particular where there are no a protons[ When
generated in situ\ however\ by the attack of BunLi on carbon monoxide at very low temperatures\
acyllithium reagents containing a protons can be formed and will attack ketones and a\b!unsaturated
ketones "0\1!addition# to give the expected products in high yield ð81JOC4519Ł[
Ar i, cyclohexanone
SmI2, –15 °C N ii, H3O+
Br +
SmI2 60%
NC
O
OH
Scheme 35
N
N
N
N
Ph
(30)
Many procedures have been published for the selective oxidation of secondary over primary
alcohols\ but not all of these have examples where the two functional groups are within the same
molecule "for a recent review see ðB!78MI 293!90Ł[ Methods that selectively oxidize the secondary
alcohol of 0\1!diols include chromium on a solid support ð89TL4674Ł and catalytic cerium"IV# in the
presence of NaBrO2 ð75BCJ094Ł[
The oxidation of alkenes or the hydrolysis of alkynes where the multiple bond is similarly
substituted or unactivated may give mixtures of products owing to regiochemical problems or over!
oxidation[ However\ terminal alkenes can be selectively oxidized to a!hydroxymethyl ketones in
good yield ð80CL0388\ 82CL0656Ł[ Regiochemical problems can be overcome when a neighbouring
group is used to control the addition to the alkene "Scheme 25# ð73JOC690Ł\ by the presence of
silicon "Equation "44## ð75TL54Ł or phosphorus ð73S0914Ł on the alkene\ or using allylic ethers or
acetates to give a!hydroxy a?!oxygenated ketones ð80CL0388\ 82CL0656\ 82JOC1818Ł[ Tertiary pro!
pargylic alcohols with a terminal alkyne undergo smooth hydration to a\a?!dihydroxy ketones using
iodine"III#\ whereas terminal alkynes give hydroxymethyl ketones ð74TL2726Ł[ A ~exible approach
to dioxygenated ketones has recently been disclosed which can be used to make a variety of systems
"Scheme 26# ð80BCJ0471\ 80JOC3018Ł[
n-C5H11 I
O
n-C5H11 i, BunLi, CO2 Amberlyst A26 F– form
n-C5H11
O O
OH ii, I2
OH
O
Scheme 36
Bearin` An Oxy`en 048
i, mcpba O
SiMe2(OR) ii, KHF2, KHCO3 n-C6H13 (55)
n-C6H13 80% Prn
Prn
OH
HO
HO
O
Scheme 37
OBn
R1
(31)
Developments have been made in the chemoselective coupling of silyl enol ethers with aldehydes
in the presence of acetals\ for example an InCl2!catalysed aldol reaction ð80CL838Ł and an organo!
aluminum!promoted ene reaction ð82TL5170Ł[ A remarkably chemoselective aldol:Mukaiyama aldol
reaction has been demonstrated by Otera and co!workers[ Thus\ in the presence of dibutyltin
ditri~ate\ aldehydes but not ketones react with silyl enol ethers to give b!hydroxy ketones[ Following
acetalization\ however\ acetals derived from ketones give b!alkoxy ketones whereas\ under the same
reaction conditions\ aldehyde acetals are recovered in high yield[ This communication would indicate
the prospect of unique selective functionalization ð89JA890Ł[ For all of these reactions\ careful
exclusion of water is important\ but Kobayashi and co!workers have developed a procedure which
allows aldol coupling reactions between silyl enol ethers and aldehydes in a mixture of water and
THF ð81TL0514Ł[ The key to the reaction appears to be the use of lanthanide tri~ates and an increase
in the scale of the reaction could make this particularly useful\ as the catalyst can be reused[
Treatment of 0\2\4!trioxane with methylaluminum bis"3!bromo!1\5!di!t!butyl phenoxide#
"MAPH# results in the cleavage of the trioxane and complexation of the resulting formaldehyde
with the metal[ The complex is stable at 9>C for several hours and is a valuable source of this
highly reactive electrophile[ It has been shown to undergo enolate hydroxymethylation and an
intermolecular ene reaction with silyl enol ethers "Scheme 27#\ both in good yields ð89JA6311Ł[
The importance of b!hydroxy ketones has meant that many non!aldol!based routes to these
systems have been developed[ The chiral ortho esters "21# react with silyl enol ethers in the presence
of a Lewis acid to give monoprotected 0\2!diketones[ Diastereoselective reduction of the ketone
gives mixtures of stereoisomers whose ratio depends on the substrate ð81T0188Ł[ In a similar method\
a combination of conjugate addition\ enolate trapping\ ketone reduction and hydrolysis of acyl
059 Dialkyl Ketones
O-TMS
O-TMS
O
MAPH
H2CO MAPH OH
O O 71%
Scheme 38
ketene acetals "e[g[\ "22## gives stereochemically enriched products ð80T864Ł[ A reduction step is also
involved in a preparation of terminal b!hydroxy ketones which relies on readily available starting
materials and a mild deprotection step "Scheme 28# ð89S0948Ł[ The presence of a silyl group can
often be considered as equivalent to a hydroxy group as the carbonÐsilicon bond can be cleaved by
oxidizing agents[ When combined with the conjugate addition of a silyl group to an enone\ this can be
used to prepare b!hydroxy ketones ð73CC18Ł[ Recently\ this has been combined with an asymmetric
hydrosilylation of enones to give optically active b!hydroxy ketones ð83T224Ł[ An elegant and widely
exploited method for the synthesis of b!hydroxy ketones is the nitrile oxideÐalkene cycloaddition
ð80COS"3#0958\ 80COS"3#0000Ł[ This produces an intermediate isoxazoline\ in which the stereochemistry
of the substituents is controlled using an appropriately substituted alkene and\ if required\ chirality
transfer can occur to other positions[ Ultimately\ the isoxazoline is converted into the desired
product "Scheme 39#[ Cyclization of allylsilanes with nitrosium tetra~uoroborate can also be used
to give isoxazolines and\ hence\ hydroxy ketones ð82JA6787Ł[
MeO2C CO2Me Ph
O O
O O Ph
O
R OMe
(32) (33)
O O O O
O O i, LiAlH4, 0 °C
(CH2OH)2, C6H6, reflux ii, SiO2, H2O, (CO2H)2
EtO EtO HO
93% 82%
Ph Ph Ph
Scheme 39
R3 R1 O OH
+
R3 N O– + R2
R1 R3 R2
N
O R2 R1
Scheme 40
A series of papers has dealt with a study of the rearrangement of epoxy silyl ethers to b!oxygenated
aldehydes "see Chapter 2[90[3[2# or ketones[ The epoxides are available in enantiomerically pure
form by use of the Sharpless asymmetric epoxidation and\ as the rearrangement is concerted\ this
leads to stereochemically pure b!silyloxy ketones[ The silyl group can be removed in situ if required[
As little as 4 mol) catalyst is su.cient to promote the rearrangement ð76TL2404Ł\ which can also
be used to construct quaternary centres "Equation 45# ð76TL4780Ł[ a\b!Epoxy ketones undergo
reductive ring opening at the a position with a number of reagents\ including NaI ð65CB2896Ł\ SmI1
ð75JOC1485Ł and PhSeNa ð76TL3182Ł to give b!hydroxy ketones[ Ring opening reactions of epoxides
with acyl anions also gives b!hydroxy ketones ðB!76MI 293!90\ 78T6532Ł[
Bearin` An Oxy`en 050
Ar
BF3•Et2O HO
(56)
O Ar 97%, 87% ee
OH O
The selective oxidation of 0\2!diols in which one of the hydroxyls is attached to a primary carbon
can be achieved using many reagents\ including trichloroisocyanuric acid ð81SC0478Ł\ H1O1 and a
tungsten complex ð80JOC4813Ł\ chromium on a solid support ð89TL4674Ł and cerium"IV# ð75BCJ094Ł[
Asymmetric reduction with baker|s yeast has been applied to cyclic and acyclic 0\2!diketones with
mixed results[ 1!Methyl!1!alkylcyclopentane!0\2!diones give preferentially the syn adducts "23#\
whereas similarly substituted cyclohexanediones favour the anti isomer\ although with more varied
stereochemical yields[ Larger ring 0\2!diones appear to be poor substrates[ For 1!monosubstituted
acyclic 0\2!diones\ stereoselectivities can also be very high\ although this is sometimes at the expense
of chemical yield ð89S0\ 80CRV38Ł[
R
O OH
(34)
R2
O O O
O O
IZn Li Li Li
Ph O
R1
(35) (36) (37) (38)
OR
O
O-TBDMS
O S O
NO2
Li
Li
(39) (40) (41)
O
O O
dabco, CH2(COSEt)2 Raney Ni
Scheme 41
051 Dialkyl Ketones
O
O
O
O hν, Ph2CO, MeOH
(57)
71% O
O
HO
BnO O
R SnBu3
(42)
Several methods are available for the direct oxidation of ketones\ including the use of iodine"III# to
prepare a!methoxy ketones ð76JOC049Ł and a mild method involving treatment with a manganese"III#
carboxylate to give a!acyloxy ketones[ A range of carboxylate groups can be introduced at the a
position using this approach ð89SC1168Ł[ This reaction has been shown to occur in high yield at the
a sp2 carbon of aryl alkyl and alkyl alkenyl ketones and to be highly chemoselective ð81S124Ł[ A
review has recently appeared on the oxidation of a\b!unsaturated ketones at the a? position ð81S124Ł[
The addition of oxygen anions to nitroalkenes is a facile process which occurs under mild
conditions[ Silylation of the resulting nitronate permits an especially mild Nef reaction\ giving a!
alkoxy ketones in high yield ð76TL4250Ł[ Nucleophilic attack at sul_nyl epoxides occurs regio!
speci_cally b to the sul_nyl group to give an intermediate alkoxide anion which collapses with
elimination of PhSOH "Scheme 31#[ Intermolecular nucleophilic attack by alkoxides is not an
e.cient process\ but intramolecular cyclization gives the corresponding cyclic ethers[ Intermolecular
acetoxylation can be achieved using Pb"OAc#3:CsOAc to give a!acetoxy ketones[ These authors
have written a recent review which covers this area ð81SL344Ł[ The treatment of a!halo ketones with
oxygen nucleophiles is one possible method for the formation of a!oxygenated ketones\ but the
outcome is very dependent on the structure of the substrate and the conditions used "for a recent
review see ðB!77MI 293!91Ł#[ Oxidative cleavage of allylic acetates with alkenes is an obvious method
for the synthesis of a!acetoxy ketones\ and many examples are known[ Terminal alkynes can be
converted into a!acyloxymethyl ketones using NaBO2:Hg"OAc#1 ð78SC1484Ł\ whilst addition to
alkynylphenyl iodonium salts under acidic or basic conditions gives similar products ð78JOC3927Ł[
As an alternative\ the addition of water to propargylic alcohols or acetates using catalytic ruthenium
ð76JOC1129Ł or NaAuCl3 ð80JOC2618Ł also gives acetoxy ketones[
O R2 R2
SOPh O– O
R2 R3O R3O
R1 SOPh
R1 R1
Scheme 42
Among the recent developments in the Mukaiyama aldol reaction enol acetates have been
shown to act as enolate donors to give b!alkoxy ketones ð81CL1928Ł[ Lanthanide tri~uoromethane
sulfonates\ reusable catalysts\ can be used for a similar transformation ð82S260Ł and TMS bis"~uoro!
sulfonyl#imide has been reported to be a more active catalyst than TMS!OTf ð82TL6224Ł[ Oxidative
Bearin` An Oxy`en 052
cleavage of 2!substituted 3\4!dihydropyrans gives g!formyloxy ketones in high yields and\ using one
equivalent of ozone\ remote\ isolated alkenes survive ð82JOC2058Ł[
A novel intramolecular reduction is part of a recent synthesis of d!acyloxy ketones[ Thus\
treatment of an iodo ester with SmI1 and an acylating agent results in rearrangement to an
equilibrium mixture of d!hydroxy ketones in which steric crowding is believed to control the direction
of the reduction "Equation 47# ð82JA4710Ł[
i, SmI2
O ii, AcCl OAc O
Ph I (58)
79%, 90% ee
Ph
O
OSiEt2Me
Scheme 43
The aldol reaction of an enol derivative with a C!0 electrophile often requires the use of formal!
dehyde\ which can be di.cult to generate from its commercially available form\ and so a number of
formaldehyde equivalents have been developed including chloromethyl benzyl ether ð78CC0523Ł
and b!trimethylsilylethoxymethyl chloride ð89SL006Ł used to introduce an alkoxymethyl and a
siloxymethyl group respectively "Equation 48#[ In a surprising reaction\ THF act as an electrophile
in the TMS!OTf!catalysed reaction with SAMP or RAMP hydrazones[ A 3!silyloxy butyl group is
introduced at the a position of the hydrazone and the ketone can be unmasked without removal of
the silyl group[ Chemical and stereochemical yields are very good ð82S0981Ł[
O O
base, ROCH2Cl
OR (59)
R = CH2CH2–TMS, Bn
053 Dialkyl Ketones
2[93[4 KETONES BEARING A SULFUR FUNCTION
O O R2
S R1
S HO
R2 R2 OH
R1 R1 R1 S
R2
(43) (44)
The two best!established methods for the synthesis of a!sulfenyl ketones are the direct sul!
fenylation of ketones or their derivatives or via substitution at a!halo ketones by a thiolate anion[
For the former\ the success of the method depends on the ability to control a number of side
reactions[ Many sulfenylating agents are known\ including thiocyanates\ sulfenyl acetates\ thios!
ulfonates\ sulfenyl chlorides\ disul_des\ thioamines and N!thioamides\ with the choice of the most
appropriate reagent being dependent on the reactivity of the enolate donor[ For example\ silyl enol
ethers frequently require the use of the highly reactive sulfenyl chlorides\ whose use may be
incompatible with other functional groups[ Conversely\ enolate anions will react readily with
disul_des[ Other problems associated with the sulfenylation of ketones include the formation of
regioisomeric mixtures\ the possibility for a\a or a\a? bissulfenylation\ a facile elimination of PhSH
from the product to give a\b!unsaturated carbonyl compounds and the greater acidity of the product
with respect to the starting material\ which means that an extra equivalent of base may be required
to compensate for proton transfer[ Additionally\ regiospeci_c sulfenylation is\ as expected\ crucially
dependent on regiospeci_c enolate generation[ The acidity of a!sulfenyl ketones means that the
introduction of further substituents at the a position is relatively easy to achieve "for a review of
much of the early work in this area see ð67CRV252Ł^ see also ð80COS"6#008Ł[ Recent developments
have lead to a number of improvements in the procedures or reagents used for the sulfenylation of
ketones[ Usually a!phenyl sulfenyl or a!methyl sulfenyl ketones are prepared as intermediates for
further elaboration^ however\ alkylation of the potassium salt of thiosulfonic acids with appropriate
alkyl halides allows access to a greater range of sulfenylating agents[ Using these thiosulfonate
esters\ one equivalent of base may be enough for e}ective reaction with ketones ð73LA148Ł[ Thio!
sulfonate esters have also been used for the sulfenylation of silyl enol ethers[ Under the reaction
conditions\ the silyl enol ether is cleaved by tetra!n!butylammonium ~uoride\ and the resulting
ammonium enolate reacts within a few minutes even at low temperatures ð78S353Ł[ For chiral
ketones\ where diastereofacially selective addition is observed\ the use of lithium amide bases or
thioamines as sulfenylating agents may be problematic because the presence of a basic amine as the
by!product can cause epimerization at the a position[ Under these circumstances\ the use of silyl
enol ethers and N!phenylthio lactams may be bene_cial ð81JOC0837Ł[ Sulfenylation of enol borinates
occurs in very high yields with phenyl sulfenyl chloride or the ester "34#[ Reaction occurs at the less
highly substituted side of the ketone and bissulfenylation occurs as a minor pathway in only one
case ð80SL034Ł[ Diastereofacial addition to an enantiomerically pure enol borinate ð80SL034Ł or tin
enolate ð75CL0798Ł gives only low selectivities\ but this may be improved using bulkier sulfenylating
agents ð75CL0798\ 81JOC0837Ł[ A recently reported reagent for the sulfenylation of silyl enol ethers
"35# appears to have a number of advantages over other reagents[ No activating agent or Lewis acid
is required to facilitate the reaction\ which proceeds without the use of very low temperatures to
give monosulfenyl ketones ð81TL5000Ł[
In many of the examples discussed above\ modern methods for regiospeci_c ketone enolization
ensure regioisomerically pure products^ however\ this is not always the case and in addition attempts
to prepare a\a bissulfenyl ketones using this approach often gives mixtures of isomers[ An alternative
procedure for a\a bissulfenylation has been developed for cyclic ketones which involves a one!
Bearin` a Sulfur 054
NTs
CO2Me Ph S
ClS N SPh
Ts
(45) (46)
carbon ring expansion[ In cases where the two a positions are substituted to di}erent degrees\ bond
migration is selective with only a small amount of the alternative isomer being formed "Scheme 33#
ð79TL3290Ł[ For acyclic ketones\ bissulfenylation can follow a two!carbon homologation\ although
the _nal hydrolysis requires the use of a strong acid "Scheme 34# ð76S492Ł[
O O
HO C(SMe)3 SMe
(MeS)3CLi (MeCN)4CuClO4
SMe
73% 60%
Scheme 44
OH O
O R1 i, BF3•Et2O, HS(CH2)3SH
i, ButLi, –78 °C O ii, 40% H2SO4, THF S R1
R2
ii, R1R2CO 60–90%
O S R2
O
Scheme 45
An experimentally simple procedure has been reported for the synthesis of a!methoxy!
carbonylsulfenyl ketones which involves neither base nor low temperatures[ Under the standard
conditions\ the thermodynamically favoured isomer predominates "Equation "59##^ however\ kin!
etically generated silyl enol ethers react regiospeci_cally to give the kinetic product ð81JOC0942Ł[
a!Thiocyanato acetophenones\ which are useful reagents for the preparation of heterocycles\ can be
prepared from acetophenones and potassium thiocyanate using iodine"III# in a one!pot procedure
ð82SC0344Ł[
O O
MeOCOSCl, 0 °C, CH2Cl2
(60)
68%
SCO2Me
Treatment of a!halo ketones with sulfur nucleophiles is a standard method for the preparation
of a!sulfenyl ketones and many examples exist in the literature ð79JA2437\ 71TL4920Ł[ Bromides\
chlorides or iodides act as substrates and organic or inorganic bases can be used to form the thiolate
anion[ A previous review has covered in detail much of the work in this area ðB!77MI 293!91Ł[ Thiols
themselves are pungent\ readily oxidizable materials which may not store for prolonged periods\
and therefore methods have been developed for their generation and use in situ from thioimidates
ð76IJC"B#0000Ł or disul_des ð78BCJ0247Ł[ Despite the presence of an easily oxidizable sul_de\
b!hydroxy sul_des\ prepared from the ring opening of epoxides by sul_des or the reduction of
a!sulfenyl esters with LiBH3\ can be oxidized to a!sulfenyl ketones using the DessÐMartin reagent
or SO2 = pyridine ð77JMC1088Ł or chloral on Al1O2 ð66TL2116Ł[
Alkenes or epoxides act as intermediates in a number of syntheses of a!sulphenyl ketones[ Thus\
regiospeci_c sulfenylation is achieved using alkenyl sul_des or alkenyl silanes as substrates\ where
the carbonyl group arises from the heterofunctionalized carbon atom "Equation "50##[ The majority
of the published examples lead to terminal phenyl sulfenyl methyl ketones\ and hydroxy and keto
groups survive the reaction conditions ð77CC0357\ 82T1900Ł[ Thiolate anions add to a!substituted
b!aryl nitroalkenes in the presence of a reducing agent to give isolable a!sulfenyl oximes which can
be hydrolysed to the corresponding ketones ð74SC332Ł[ The bisfunctionalization of alkenes to
sulfenyl ketones is not a trivial process but one that has been achieved via initial electrophilic attack
with dimethyl"methylsulfenyl#sulfonium tetra~uoroborate[ The resulting sulfonium ion can be trap!
ped with DMSO\ and\ after elimination of dimethyl sul_de\ a!methyl sulfenyl ketones are obtained
in good yield[ Terminal alkenes give a!methyl sulfenyl methyl ketones and 0!phenyl propene gives
055 Dialkyl Ketones
0!phenyl!1!methyl sulfenyl propanone "Scheme 35# ð71JA2117Ł[ It might be anticipated that addition
to nonsymmetric\ dialkyl alkenes or alkynes would give mixtures of regioisomers[ This has been
observed with a related method "Equation "51##\ although again in this case terminal alkynes give
good yields of a!sulfenyl methyl ketones ð77TL1270Ł[
O
R1 X
R4S (61)
R3
R2 R3 R1
R2
X = SR5, SiR63
Me
S+ O
Me2S+SMe•BF4– Me O Pri2NEt
Ph Ph
then DMSO 80%
Ph SMe
SMe
Scheme 46
+
O SPh
i, ArNH(SPh)BF3–
Prn + (62)
ii, H3O+
SPh O
30% 40%
Ar = C6H4NO2-p
Several procedures for the regioselective synthesis of a!sulfenyl ketones have been reported which
rely on a homologation reaction[ Phenylthiotrimethylsilylmethyl lithium adds e.ciently to esters\
but not to acid chlorides or to anhydrides[ On exposure to silica gel\ the adducts lose the TMS
group via a protiodesilylation to give a!phenyl sulfenyl methyl ketones ð70TL1792Ł[ A methyl sulfenyl
methyl group can also be introduced using the reaction between the ketene silyl acetal of ethyl
a!methyl thioacetate and an acid chloride followed by a decarboxylation "Scheme 36# ð68JOC3506Ł[
Decarboxylation forms part of another one!pot synthesis of sulfenyl ketones "Equation "52##[ In
this case\ the method works best for a!substituted ketones ð67BCJ2997Ł[ A bissulfur!stabilized anion
adds to aldehydes in high yield\ and the adducts undergo an acid!catalysed rearrangement "Scheme
37# ð68JCS"P0#0963Ł[ Conjugate addition of an alkyl thiol to the vinyl phosphonate "36# generates an
ylide which reacts with aryl aldehydes as shown in Scheme 38 ð72S221Ł[
TMS-O O
MeS OEt H 3O + O
C7H15COCl
C7H15 OEt SMe
O-TMS 57% C7H15
SMe
Scheme 47
O O
Ph2S2, HMPA, NaI, 160 °C
(63)
CO2Me 49% SPh
Another method which does not require regiospeci_c enolate generation is the Rh1"OAc#3!cat!
alysed addition of thiophenol to a!diazo ketones[ As the diazo ketones are readily available from
the corresponding acid chloride and diazo alkanes\ and the sulfenylation occurs in high yield\ the
transformation could be widely applicable\ limited only\ perhaps\ by the need to generate potentially
hazardous diazo alkanes on a large scale[ The reaction can be used to make nonterminal sulfenyl
ketones by use of the appropriate diazo ketone "e[g[\ "37## ð71TL1498Ł or heterocyclic ketones
following an intramolecular reaction "Scheme 49# ð89T5490Ł[ In the presence of phenyl sulfenyl
chloride\ diazo ketones are converted into the adducts "38#[ These undergo inter! "Scheme 40# or
Bearin` a Sulfur 056
O
R1 R1 OH p-TsOH, C6H6
R2CHO R1
PhS Li PhS R2
PhS PhS R2
SPh
R1 = H, alkyl
Scheme 48
intramolecular FriedelÐCrafts reactions to replace the chloride with an aryl group at the a position
ð72TL006Ł[ Aryl sulfenyl alkyl boronate esters "e[g[\ "49## can be deprotonated adjacent to the sulfur\
and the resulting anion reacts with esters[ Under the reaction conditions\ the boron group migrates
from carbon to oxygen and the enol borinate is hydrolysed to the ketone using acid ð71OM179Ł[ A
review has some examples of sulfur!stabilized anions ðB!76MI 293!90Ł[
O
O
Ph N2
B
Ph O
SPh
(48) (50)
O
O Li CO2Me O
CO2Me
N2 Rh2(OAc)4 CO2Me
S N2
58% 34% S
SH
Scheme 50
O O
O PhSCl C6H6, SnCl4
Cl Ph
N2 Ph Ph
Ph 96% 70%
SPh SPh
(49)
Scheme 51
Anions stabilized by an adjacent sul_nyl group have been used in a number of syntheses of
a!heterofunctionalized ketones[ For example\ the treatment of "40# with lithium diisopropylamide
"LDA#\ followed by an aldehyde or ketone\ gives a b!chloro alcohol which could be elaborated in
a number of di}erent ways[ In one example\ thermal elimination of phenyl sulfenic acid followed
by epoxidation gives an epoxide\ which can be readily attacked by thiolate anions to give a!sulfenyl!
a?!oxygenated ketones "Scheme 41#[ An alternative procedure\ but one which can give structurally
complementary products\ involves a Darzens condensation of chlorosulfoxides with aldehydes or
ketones to give a\b!epoxy sulfoxides[ Nucleophilic attack at such systems is directed towards the b
position to give an alkoxide anion which can react further by spontaneous elimination of the geminal
sul_nyl group[ Dioxolanes remain una}ected by the reaction conditions\ and thiols containing
esters\ heterocycles or alcohols can be used in addition to simple alkyl or aryl thiols "Scheme 42#[
Further examples of the use of haloalkyl aryl sulfoxides for the synthesis of a!heterofunctionalized
aldehydes and ketones can be found in the review ð81SL344Ł[
057 Dialkyl Ketones
O O OH
i, LDA, –60 °C
Cl R2
S Cl S PhMe, 110 °C
Tol Tol R3
ii, R2R3CO
R1 R1
(51)
OH OH
R2 R2 O
Cl VO(acac)2, ButO2H, C6H6 Cl R4SNa, EtOH
R3 R3 R1 R3
O
R2
R1 SR4 OH
R1
Scheme 52
i, LDA, –60 °C
O
O
Cl ii, MeCHO PhSO NaSCH2CO2Me, EtOH Ph
Ph
SOPh iii, KOH, MeOH
Ph S CO2Me
Scheme 53
2[93[4[0[1 b!Functionalized and more remotely substituted SH! and SR!functionalized ketones
There appear to be fewer published methods for the synthesis of b and more remote sulfenyl
ketones\ although the thio analogue of the Mukaiyama reaction using chloroalkyl sul_des and silyl
enol ethers "Scheme 43# has been used with some success in this regard ð68TL1068Ł[ A number of
Lewis acids have been shown to promote the reaction\ which is characterized by high regioselectivity
at the silyl enol ether and a tolerance for a number of functional groups\ including alkyl halides\
esters\ ketones\ alkenes and silyl ethers ð77T3196Ł[ The chloro sul_des are easily prepared from the
corresponding sul_des[ Since these initial reports\ other sources including dithioacetals ð74CL0760\
89JOC4855Ł\ vinyl sul_des ð75TL2918Ł and a!nitro sul_des ð76CC836Ł of the presumed thionium
intermediate have been disclosed[ Thionium ions a to a carbonyl "e[g[\ "41## also act as substrates
for silyl enol ethers to give products in which the sulfenyl group is both a and b to carbonyl groups
within the same molecule ð73CL0420Ł[ b\b!Disulfenyl ketones can be prepared by an analogous
Mukaiyama reaction between cyclic or acyclic silyl enol ethers and trimethylthio orthoformate
ð74TL5402Ł and from the conjugate addition of propane!0\2!dithiol to a\b!ynones ð81JOC6238Ł[
OSiR43
SR2 + SR2
SR2 R3 O
R1 Cl R1 R1 R3
Scheme 54
O
+
SAr
(52)
The number of synthetically useful homoenolate anion equivalents has been increasing steadily
since the 0879s\ and some of these have been shown to react with sulfenylating agents to give b or
more remote sulfenyl ketones[ Much of the work in this area has been the subject of the review
ðB!76MI 293!91Ł[ Among the preparations of stable sulfur ylides "i[e[\ "42## one of the more recent is
perhaps the most direct\ involving coupling of a 0\2!dicarbonyl compound with the CoreyÐKim
reagent ð89CPB2203Ł[
The sul_nyl epoxide "43#\ prepared analogously to that shown in Scheme 42\ can be used to
prepare b!sulfenyl or a\b?!disulfenyl ketones\ depending on the reaction conditions "Scheme 44#
ð81SL344Ł[ b\g!Epoxy nitro compounds\ which are readily available from allylic nitro compounds\
Bearin` a Sulfur 058
undergo a base!catalysed ring opening and double!bond rearrangement accompanied by dis!
placement of the nitro group\ to give b!sulfenyl ketones "Scheme 45# ð89JOC484Ł[
O O
R1 R2
+ SMe
(53)
O O O O O O
(54)
Scheme 55
O PhS
O 2N
O
O
i, MeNO2, H2NC2H4NMe2, C6H6, reflux PhSH, Et3N, DMF, 70 °C
Scheme 56
The lithium enolates of cyclic ketones have recently been shown to undergo a 0\3 addition to
a\b!unsaturated sulfoxides in good yield[ Reduction of the sul_nyl group then givesg!sulfenyl ketones
ð82JOC5365Ł[ Earlier\ this same conjugate addition had been achieved for acyclic ketones using the
lithium enolate of acetone or via the dianion of ethyl acetoacetate and a subsequent decarboxylation
ð72TL394Ł[ As an alternative to this\ episulfonium ions\ generated from alkenes ð72TL850Ł or
1!phenyl sulfenyl alcohols ð81CL128Ł react with silyl enol ethers to give similar products[ In the latter
case\ reaction takes place at the most!substituted terminus of the episulfonium ion^ homochiral
alcohols have been used to give optically active products "Equation "53##\ and the reaction could be
used to generate compounds with adjacent quaternary centres[ The conjugate additions of 1!lithio!
0\2!dithiane ð76S0015\ 78T6532Ł and a!lithiosul_des "Equation "54## ð66TL0850Ł to a\b!unsaturated
ketones has also been reported[ The synthesis of sulfenyl ketones has been part of a previous review
ð66HOU"6:1C#1206Ł[
O-TMS
O
OH Pri
H SPh Pri (64)
TiCl4 H SPh
Ph
Ph
100% ee 92%, 100% ee
O
O
SPh ButLi, HMPA
+ (65)
57%
SPh
069 Dialkyl Ketones
2[93[4[1 Higher!coordinated Sulfur!functionalized Ketones
Oxidations of a!sulfenyl ketones "see Section 2[93[4[0[0# can be an excellent method for the
synthesis of a!sul_nyl ketones\ and one for which a number of reagents are known[ This is perhaps
the most frequently used method\ particularly where the products are to be thermolysed to the
corresponding a\b!unsaturated carbonyls[ However\ direct sul_nylation of ketones or their deriva!
tives is a viable alternative\ and a number of sul_nylating reagents have been developed\ including O!
alkyl aryl sul_nates ð64TL810\ 82JOC0468Ł\ aryl sul_nyl aryl sulfones ð82SC0404Ł and sul_nyl chlorides
ð71S172Ł[ Interest in the synthesis of a!sul_nyl ketones "b!keto sulfoxides# has greatly increased as
the importance of a homochiral sul_nyl group in chirality transfer reactions has become widely
recognized ðB!72MI 293!91\ 80COS"5#022Ł\ and optically active sul_nates capable of reacting with ketone
enolates are becoming available ð75CL54\ 81JOC6124\ 82JOC3444Ł[ The other widely recognized method
involves the reaction of a sulfoxide stabilized anion with an acid derivative\ and many similar
procedures have been developed to achieve this ðB!77MI 293!92\ B!77MI 293!93\ 80COS"5#022\ 80JOC217Ł[
Anions stabilized by an adjacent sul_nyl group have been used in a number of other syntheses of
a!heterofunctionalized ketones[ For example\ treatment of chloromethyl phenyl sulfoxide with LDA
and an aldehyde gives a highly functionalized adduct which can\ on further exposure to LDA\
undergo elimination of HCl to give an a!sul_nyl ketone "Scheme 46# ð89BCJ0155Ł[ On treatment
with a ketone\ however\ a di}erent mechanistic pathway results[ Under these conditions "Scheme
47#\ a 0\1 elimination of HCl is not possible and so\ on the basis of the products formed\ a 0\0
elimination is postulated to give a sul_nyl carbene which rearranges to give the observed products
ð81TL6070Ł[ The di}erence in the relative migratory aptitude of the two groups adjacent to the
carbene will determine the selectivity and\ hence\ the usefulness of the procedure[
LDA, –65 °C O OH
O n-C9H19CHO LDA (3 equiv.) O O
S
S Cl Ph n-C9H19 S
Ph 98% 95% Ph n-C9H19
Cl
Scheme 57
O Ph Ph
O Ph
S Cl S O S O
Li OH LDA : OLi H2O
Cl
100% 70%
O
Ph S
O
Scheme 58
N
CO2H O
O N SO2Me
Im2CO LiCH2SO2Me
N N
N 67%
Scheme 59
One method for the preparation of b!keto sulfones which may be particularly attractive for large!
scale work involves the oxidation of a!sulfenyl ketones "see Section 2[93[4[0[0# with Oxone ð76SC712Ł[
Other methods for the synthesis of a!sulfonyl ketones include one of unsaturated sulfonyl ketones
using a carbanion!accelerated Claisen rearrangement "Scheme 59# ð71JA3861Ł and a recently reported
procedure which occurs in the absence of base "Equation "55##[ In the latter case\ branching at the
a position of the aldehyde leads to a reduction in yield ð81TL0020Ł[ Two procedures involving
conjugate addition reactions have been used as routes to a!sul_nyl or a!sulfonyl ketones[ The
Michael addition of diethyl amine to allenic sulfoxides generates an unstable enamine "Scheme 50#
ð71LA0985Ł\ and alkenyl selenoxides undergo hydrolysis via conjugate addition of water or alcohols
"Scheme 51# ð72JOC2966Ł[
PhSO2 O
ONa KH, HMPA, 50 °C O
PhSO2
• 65% PhSO2
80%
Scheme 60
O O
S O SnCl2 O O O
Ar + S (66)
Ph 80% Ph Ar
N2
Scheme 61
Scheme 62
O
O O– CO2Bn Rh2(OAc)4
S (67)
62% N CO2Bn
Me NH-BOC
Me
(55) BOC
O LiCH2SO2NHR O
SO2NHR (68)
BOC-N NMeOMe 98% BOC-N
O O
O O O O
SCl SNEt2
S Cl Cl
SO2NHMe O S S
(56) (57) (58) (59)
i, PCl5 or SOCl2
(69)
ii, NH4OH
O O
SO3H SO2NH2
A multistep but high!yielding synthesis of b!sul_nyl ketones has been reported which appears
~exible enough to be used for a number of di}erent systems "Scheme 52# ð68TL2056Ł[ Potentially
also this could be used to prepare b!sulfonyl ketones[ Propargylic sulfones can be used to prepare
a! or b!sulfonyl ketones depending on the reaction conditions[ On simple treatment with NaOMe\
followed by dilute HCl\ a!sulfonyl ketones were isolated in excellent overall yield[ In the presence
of a mercury"II#\ salt however\ the regioselectivity of the hydration is reversed to give b!sulfonyl
ketones ð78TL6278Ł[
i, BunLi, –40 °C
i, R1SH, Et3N ii, R2I
O ii, HS(CH2)3SH, BF3•Et2O S iii, Tl(ONO2)3
O
O NaIO4 R1
S R2
R1S R2 76–93%
O
Scheme 63
The conjugate addition of enolate anions to alkenyl sulfoxides has been used sparingly despite its
being potentially the most direct route to g!sul_nyl ketones[ Ten years ago it was shown that the
acetone enolate or the dianion derived from ethyl acetoacetate could be used in this manner
ð72TL394Ł\ and since then enolates derived from acyclic ð72JOC803Ł or cyclic ð82JOC5365Ł ketones
have been shown to behave in the same way[ a\b!Unsaturated sulfones also serve as Michael
acceptors in their reaction with SAMP and RAMP hydrazones to give g!sulfonyl ketones[ Good
diastereoselectivity is observed in the addition of a homochiral hydrazone to b!substituted sulphones
ð82T0710Ł[
Bearin` a Selenium or Tellurium 062
2[93[5 KETONES BEARING A Se OR Te FUNCTION
O O
O O
R2 R1 R2
R1
R1 R2 Se R1 R2
SeR3 R3
O
Scheme 64
The a!selenylation of carbonyl groups was _rst studied independently by three research groups
ð62CC584\ 62JA4702\ 62JA5026Ł\ although the substrates varied from enol acetates\ to enolates\ and to
ketones\ respectively[ In situ enolization and selenylation of ketones is obviously the most direct
ð62JA5026\ 64JA4323Ł and can be surprisingly chemoselective with esters\ silyl ethers\ isolated alkenes\
epoxides and ketals being some of the groups that remain una}ected ð67JOC3441\ B!76MI 293!93Ł[ The
reaction proceeds via the enol form of the ketone\ and\ in di.cult cases\ enolization may be
enhanced by the presence of hydrogen chloride or an acidic ion exchange resin ð67JOC3441Ł[
N!"Phenylselenyl#phthalimide also requires the presence of acid "one equivalent of p!TsOH# in order
to react directly with ketones[ Selenylation occurs preferentially at the more!substituted side of a
cycloalkanone\ and 1!cyclohexenone gives 5!phenyl selenyl 1!cyclohexenone in 49) yield
ð82TL6644Ł[
The requirement in most of these methods for acidic conditions to promote enol formation is
incompatible with the presence of some functional groups\ and it may be more practical to use a
preformed enol derivative[ This can lead to a complementary or more regioisomerically predictable
outcome because of the myriad of methods that are available for regioisomeric ketone enolization[
Enol acetates ð62CC584Ł\ enol borinates ð80SL034Ł and silyl enol ethers ð66S763Ł\ the last even in the
presence of ketones ð70JACS2359Ł\ undergo direct reaction with PhSeCl or PhSeBr\ to give the
corresponding a!phenyl selenyl ketones[ With silyl enol ethers two new selenium species\ "59# and
"50#\ have been shown to give high yields ð81TL5000\ 82CC0520Ł[ The latter introduces an acyl seleno
group at the a position[
NTs
Ph Se O
N SePh R SeCl
Ts
(60) (61)
Metal enolates have also been used for the formation of a!phenyl selenyl ketones\ and the greater
reactivity of such systems may allow for the use of the less reactive\ but more stable\ diselenides as
the selenylating agents[ In some examples\ however\ this procedure is complicated by the estab!
lishment of an equilibrium reaction owing to the selenophilic nature of the selenate anion "Equation
"69##[ Lithium enolates generated by direct deprotonation ð62JA4702\ 64JA4323Ł or conjugate addition
ð64JA4323Ł and aluminum or zirconium enolates generated by conjugate addition ð79TL0386Ł are
among those that have proved e}ective in their reaction with selenylating reagents[
O
OM
+ PhSeSePh R2 + PhSeM (70)
R2 R1
R1
SePh
M = metal
The most common selenylating agents\ Ph1Se1\ PhSeCl and PhSeBr have already been mentioned\
although the last occasionally acts as a brominating agent[ There are\ however\ a number of other
reagents or methods that can be used[ Perhaps the most cost e}ective\ involves the reaction of an
063 Dialkyl Ketones
enolate with selenium metal to give a selenate anion[ This can then be alkylated on selenium with a
variety of alkyl halides to give less common a!selenyl ketones ð79TL2532Ł[
Several published procedures do not require the use of a strong base[ Thus\ PhSeBr\ generated in
situ from the electrolysis of Ph1Se1 reacts directly with ketones ð79TL0752Ł\ and the oxidation of
diselenides with SeO1 gives a more electrophilic selenylating species which can also react directly
with simple ketones ð71TL3702Ł[ A selenylation which is promoted by acid!catalysed enol formation
employs 1!pyridyl selenyl bromide[ Prior work had indicated that the pyridyl group would enhance
selenoxide elimination when compared to phenyl and\ as expected\ yields of a\b!unsaturated car!
bonyl compounds were increased by approximately 19) for otherwise identical reactions
ð71TL1094Ł[ A later paper from the same group demonstrated that ketone enolates and silyl enol
ethers react with the same reagent ð73JOC2685Ł[ 0\2!Diketones or 0\2!keto aldehydes are selenylated
at the central position with PhSeCl in pyridine ð70JOC1819Ł or selenium metal ð70TL2932Ł[ Remark!
ably\ ketones protected as cyclic acetals react directly to introduce a phenyl selenyl group at the a
position without loss of the protecting group ð68S871Ł[
Diazo groups have been involved in two conceptually di}erent syntheses of a!selenyl ketones[
Seleno esters\ which are readily available from the corresponding carboxylic acids\ undergo insertion
into diazomethane to give terminal a!methyl selenyl or a!phenyl selenyl ketones "Equation "60##
ð74T3648Ł[ Alternatively\ cyclic and acyclic a!diazo ketones undergo spontaneous a\a addition of
PhSeCl\ PhSeBr or PhSeOAc to give bis heterofunctionalized adducts "e[g[\ "51#\ XCl\ Br\ OAc#[
Elimination of either of the a substituents is possible under di}erent conditions "Scheme 54#
ð74JCS"P0#1082Ł[ a!Phenyl selenyl a\b!unsaturated ketones are available using a more convenient
procedure via the addition of PhSeCl to enones in the presence of base ð74T3770Ł[
O CH2N2, CuI O
SePh (71)
SePh 55%
O O O
SePh
Cl H2O2 Li2CO3 SePh
X
82% 77%
(62)
Scheme 65
ddq = 2,3-dichloro-5,6-dicyano-1,4-benzoquinone
Scheme 66
Terminal alkenes undergo Markovnikov addition of PhSeBr to give bromo selenides "Scheme
56#[ Subsequent treatment with silver"I# in DMSO results in displacement of the bromide by the
Bearin` a Selenium or Tellurium 064
solvent to give a sulfonium salt which\ on exposure to Et2N\ gives a terminal a!selenyl ketone[ The
reaction may go through the episelenonium ion "52# as the isomeric bromo selenide "53# gives the
same a!phenyl selenyl ketone rather than a selenyl aldehyde ð67TL1150Ł[ An identical transformation
has been achieved using PhSeOSnBu2 or "PhSe#1O generated in situ ð70BCJ2099Ł[ With these last two
reagents\ the proportion of a!selenyl aldehyde formed can be higher\ indicating poor regiochemical
control during the addition[ In the oxyselenylation of allylic alcohols\ ethers or acetates\ addition
to the alkene was predictable and consistent\ with the selenyl group becoming bonded to the
terminus of the double bond adjacent to the pre!existing oxygenation "Equations "61# and "62##[
The regioselectivity of the addition is lower in homoallylic ethers ð67TL0166\ 70BCJ2409Ł[ Addition of
PhSeBr to alkenes in a protic solvent has been shown to result in isolable alkoxy alkyl selenides
"e[g[\ "54##[ Oxidation at selenium to the selenoxide was followed by a thermally catalysed rearrange!
ment to the a!phenyl selenyl ketone ð67TL688Ł[ Vinyl selenides can also be oxidized to a!selenyl
ketones ð79CC840Ł[ a!Chloro sul_des are valuable sources of the thionium ion and the corresponding
selenides can be prepared as shown in Equation "63# ð78TL1554Ł[
Scheme 67
Ph
SePh OEt
Se+
Br n-C5H11 SePh
Pri
Pri
(63) (64) (65)
O
PhSeOSnBu3
AcO Ph AcO Ph (72)
73%
SePh
TBDMS-O O
TBDMS-O PhSeOSePh
Ph (73)
Ph 89%
SePh
O
O Cl pyridine
Cl Se
Se Ar R (74)
Ar R
Cl
Selenium\ like sulfur\ has the ability to stabilize adjacent carbanions[ In fact\ the di}erence in the
acidity between the a protons of otherwise identical sul_des and selenides may be as little as 0Ð1
pKa units[ The two most common methods for the synthesis of a!selenyl carbanions are the direct
deprotonation of selenides ð68JACS5527Ł and metalÐselenium exchange in diseleno acetals
ð58AG"E#349Ł\ and using di}erent electrophiles a number of remote selenyl ketone substitution
patterns can be constructed[ Reactions with acid derivatives ð65TL342Ł or aldehydes lead directly\
or following oxidation\ to a!selenyl ketones[ A number of recent reviews have dealt with the synthesis
and reactivity of selenium!stabilized anions ð79T1420\ B!75MI 293!93\ B!76MI 293!94\ B!76MI 293!95Ł[
The conjugate addition of selenol anions to a\b!unsaturated ketones can be facilitated by a
number of di}erent reaction conditions[ Using base catalysis\ benzeneselenol adds as its potassium
ð67TL4976Ł or sodium salt ð62TL0868Ł[ The former is generated from PhSe!TMS and KF\ but this silyl
selenide can react directly with enones using PPh2 ð67TL4980Ł or TMS!I ð68TL3078Ł[ Neutralization of
PhSeNa with a slight excess of acetic acid allows conjugate addition to occur under mildly acidic
conditions ð79S553Ł[ Aluminum and titanium complexes have also been shown to promote the
addition of selenate ions to enones ð74TL5320Ł[ In a related transformation\ ketals derived from
065 Dialkyl Ketones
b!amino ketones undergo direct substitution of the amino group to give a selenide "Equation "64##
ð79JA1345Ł[ In the presence of a Lewis acid\ seleno acetals ð73TL3330Ł or selenyl orthoformates
ð74TL5402Ł lose a selenate group to generate monoselenyl! or bisselenyl!stabilized carbocations\
respectively[ These react in situ with silyl enol ethers to give b!monoselenyl or bisselenyl ketones\
respectively "Equation "65##[
O O PhSeNa, RuCl3 O O
NMe2 SePh (75)
98%
O-TMS O SePh
(PhSe)3CH, SnCl4
SePh (76)
97%
Two procedures for the synthesis of g!selenyl ketones have been published which use readily
available starting materials[ The _rst involves ring opening of cyclopropyl ketones or
bicycloðn[0[9Łalkanones by phenyl selenide ð67TL0538Ł[ For the second\ the well!known ability of
selenate anions to cleave esters or lactones is exploited to transform 1!acetyl!3!butyrolactone into
4!phenylselenyl!1!pentanone by nucleophilic attack at the 3 position of the lactone "Equation "66##
ð66TL3250Ł[ Both of these methods would seem suitable for application to more complex systems[
O O
PhSeNa, DMF, 110 °C O
O SePh (77)
92%
Until recently\ there appeared to be little interest in the use of organotellurium compounds in
organic synthesis[ This situation is slowly changing\ but there are still very few reports describing
the synthesis of isolable tellurium!substituted ketones[ a!Phenyl telluro ketones have been prepared
by the reaction of ketone enolates with PhTeI[ The products decompose rapidly in light and air\
but can be handled in an inert atmosphere[ The application of other procedures for the synthesis of
a!selenyl ketones\ for example the reaction between silyl enol ethers and selenyl halides and the
displacement of halo ketones by selenate anions\ did not work for telluro ketones ð76S0985Ł[ Ketals
derived from a!bromo ketones\ however\ will undergo displacement of the halide with PhTeNa
ð75JCS"P0#0872Ł[ Diphenacyl tellurides or phenacyl tellurides have been prepared from reduction of
the dichloro derivatives "55# "R0 Ar\ ArCOCH1# "see Section 2[93[5[1# ð75OM316Ł and the diphen!
acyl tellurides can also be prepared from the reaction of bis"triphenylstannyl#telluride with phenacyl
bromide ð89TL5180Ł[ Tellurium salts can be prepared from dialkyl tellurides and phenacyl halides[
Their ylides give alkenes on reaction with carbonyl compounds ð77JOC3751Ł[
Conjugate addition of a phenyl telluro group to cyclic and acyclic a\b!unsaturated ketones can
be achieved using PhTeAlBui1[ The products are slightly air sensitive but can be isolated[ The
intermediate aluminum enolate can be used in aldol reactions to generate more heavily functionalized
b!telluro ketones "Scheme 57# ð78CL596Ł[ A recent review has dealt with the use of tellurium reagents
in organic synthesis ð80S682\ 80S786Ł[
Cl O
Cl
Te
R Ar
(66)
Bui2Al O OH
O O
PhTeAlBui2 n-C3H7CHO
76%
TePh
TePh
Scheme 68
Bearin` a Selenium or Tellurium 066
2[93[5[1 Higher!coordinated Se! or Te!functionalized Ketones
Although higher!coordinated selenium species are not uncommon\ very few of these have a
proximal aldehyde or ketone group[ The main exception to this are the b!keto selenoxides "a!selinyl
ketones#\ formed as intermediates during the oxidative elimination of selenyl aldehydes or ketones
"see Chapter 2[90[5[0 and Section 2[93[5[0# to a\b!unsaturated carbonyl compounds[ This trans!
formation has proved particularly successful because the syn elimination of benzene selenic acid
occurs at room temperature\ a process which has been studied by NMR ð74T3660Ł[ Therefore\
b!keto selenoxides can be isolated in only a few speci_c cases] where there is steric crowding at the
carbon b to the selenoxide\ where there are no b!hydrogen atoms\ or where the selenoxide and its
b!hydrogen cannot adopt the correct syn conformation[ The more highly oxidized selenones are
even less well known ðB!75MI 293!92Ł[ Direct introduction of a selenoxide is possible with phenyl
selinyl chloride\ although again elimination occurs without isolation of the a!phenyl selinyl ketone
ð64JA4323Ł[ Selenium oxychloride reacts with phenacyl chlorides to give the adducts "56# ð77TL0288Ł[
O Cl Cl O
Se
Ph Ph
(67)
On simple treatment with ketones\ PhSeCl2 acts in a manner analogous to PhSeCl except that the
product contains a tetravalent selenium group "e[g[\ "57##[ Further transformation of the product
can result in the enone\ via the selenoxide\ or the selenide "Scheme 58# ð74TL5274Ł[ Stabilized
selenonium and tellurium ylides\ "e[g[ "58## can be prepared by the reaction between selenium
dichlorides ð61JOM"31#288Ł or selenoxides or telluroxides ð79BCJ706Ł and 0\2!diketones[
O
O
Ar2Se
PhCl2Se
O
(68) (69)
O O O
NaHCO3 thiourea
R1 PhCl2Se R1 PhSe R1
50–97% 71–99%
R2 R2 R2
Scheme 69
a!"Aryldichlorotelluro#ketones "i[e[\ "69## have been prepared by the reaction between an aryl
tellurium trichloride and either a ketone or silyl enol ether[ The yields are typically quite high
"79Ð099)# ð75OM316\ 76SC332\ 82CL450Ł[ Alkyltellurium trichlorides react only poorly with aromatic
ketones but give much higher yields with their silyl enol ethers ð80OM0067Ł[ Cycloalkanones give
either the dichlorides "60# or the trichlorides "61# with TeCl3 depending on the ketone used
ð75OM316Ł[ Silyloxy cyclopropanes undergo a regioselective ring opening with TeCl3 to give either
b!trichlorotelluro ketones or the corresponding dimers depending on the amount of metal chloride
used "Scheme 69# ð80TL118Ł[
O Cl Cl O O
O
Te TeCl3
TeCl2Ar
O O
O NH3Cl (RCO)2O, DMF (cat.), 55 °C O NHCOR
N N (78)
50–99%
R = Me, Et, Ph
O R2NH2 O R2 O
Br N (80)
R1 R1 R1
O O CHO
BzO Br MeCN, reflux BzO N
+ Ph Ph
N OMe (81)
91%
BzO BzO
The transformations outlined above demonstrate that useful direct aminations of a!halo ketones
exist\ but\ particularly for the introduction of an NH1 group\ a number of alternatives exist[ For
Bearin` a Nitro`en 068
example\ reduction of a!azido ketones "see Section 2[93[6[2# gives primary a!amino ketones ð74LA674\
75JOC2263Ł[ The same products can be obtained from the reaction between a!bromo ketones and
hexamethylene tetramine "Equation "71##\ although the strongly acidic conditions required to hydro!
lyse the intermediate adduct might limit the opportunities for its use ð53RTC0936\ 71JHC58Ł[ The
allylic chlorides "62# "R0 H\ Cl# react in an SN1 manner with LiN!TMS1 to give protected amino
ketones ð82JOC6339Ł[
O O O O
i, hexamethylene tetramine
(82)
Br Br ii, HCl, EtOH Br NH3Cl
O-TMS
R Cl
(73)
Potassium phthalimide ð57AG"E#808\ 57JPR01\ 80COS"5#54Ł and sodium diformylamide ð89S504Ł are
powerful nitrogen nucleophiles which readily displace halides[ The latter has the advantage that one
or both of the formyl groups can be removed selectively "Scheme 60#[ Although no experimental
details were given\ the monoformyl derivatives "63# were alkylated at the a position to give products
that could not be made by direct substitution[ The a!alkylation of a!amino ketones has\ however\
been studied by other groups and full details are available[ As might be expected\ the presence of
an electron!de_cient nitrogen "amide or carbamate# favours deprotonation between carbonyl and
amino groups "Equation "72## and the resulting enolate can be trapped and isolated as the silyl enol
ether ð79JOC1296Ł[ Later papers by Muchowski and co!workers explored the reactivity of these
enolates with a number of alkylating agents ð75JOC2263\ 80CJC1948Ł[ These researchers demonstrated
that the monoanions of N!formyl and N!BOC amino ketones react with primary and secondary
alkyl\ benzyl and allyl halides to give the a!substituted adducts in\ usually\ good yield "Equation
"73##[ The activating groups are easily removed\ and\ therefore\ the method can be used to prepare
a series of a!alkyl a!amino ketones[ As already discussed\ however "see Chapter 2[90[6[0[0#\ an
N!8!phenyl ~uorenyl "PhFl# protecting group prevents racemization at the a position during treatment
with a variety of reagents[ In fact\ it does so to such an extent that deprotonation occurs regio!
speci_cally at the a? position "Equation "74## to give the isomeric a?!alkyl a!amino ketones
ð77JA6336Ł[
O H
NaOH, EtOH N
Ar CHO
O CHO MeCN, RT, 2 h O CHO 91–98% (74)
Br + NaN N
Ar 87–98% Ar CHO HCl, EtOH
CHO O
91–99%
NH3Cl
Ar
Scheme 71
O H
O H i, NaH
N
N Ph R (84)
Ph R ii, BunI
Bun
R = CHO, 45%
R = BOC, 60%
079 Dialkyl Ketones
O O
i, KN(TMS)2
ii, allyl bromide
(85)
85%
N N
PhFl H PhFl H
In a rather speci_c example of amino ketone monoalkylation\ and one which goes via a fun!
damentally di}erent mechanism\ allyl!substituted imines are subjected to a thermally catalysed
rearrangement[ Two competing pathways\ a ð2\2Ł sigmatropic rearrangement to give the N!allyl
ketone "64# or a 0\1!allylic transposition to give "65# are theoretically possible "Scheme 61#[ In the
end\ only the latter was observed\ to give a!amino!a!allyl ketones in reasonable yield[ A number of
N!functionalized imines\ such as "66# and "67#\ rearrange in the same way to give compounds
suitable for further synthetic elaboration[ Propargylic imines rearrange as shown in Equation "75#
ð89TL1166Ł[
R1 O HO R1 O
∆
R2 R1
R2 N
BnHN R2 NBn
Bn
(76) (75)
Scheme 72
OH O
TMS
(86)
58%
TMS
NBn NHBn
OH
OH
N
N
OMe
CO2Me
OMe
(77) (78)
Just as the reduction of amino acid derivatives is an excellent method for the preparation of
amino aldehydes "see Chapter 2[90[6[0[0#\ their reaction with organometallic reagents to give amino
ketones has been equally widely exploited[ Most conveniently\ Rapoport and co!workers have shown
that amino acids in which the amino group is protected as an amide\ carbamate or sulfonamide can
be used directly in such transformations[ The acidity of the carboxyl and amino groups must be
compensated for by the use of an excess of the organometallic reagent\ but this\ at least in part\ can
be done with relatively cheap organolithium reagents "Scheme 62#[ Very little tertiary alcohol was
formed\ and\ despite the use of at least three equivalents of a strong base\ no racemization at the a
position was observed ð72JOC1159\ 73JA0984Ł[ The same group had earlier shown that N!acyl a!amino
acid chlorides were also susceptible to attack by Grignard reagents to give the corresponding
ketones[ Using this approach\ the addition of a second equivalent of Grignard reagent to give a
tertiary alcohol may be a competing process[ In those cases where this is a problem\ stabilization of
the tetrahedral intermediate by intramolecular chelation can result in an improved yield of the
ketone[ This has been achieved using 1!pyridyl thioesters ð71TL1422Ł\ although in one direct com!
parison these were shown to be less e}ective than N\O!dimethyl hydroxamates or acyl oxazolidines
ð74JOC2861\ 75JCS"P0#0784Ł[
The reaction of an acylating agent with an amino acid to introduce an alkyl group and form an
alkyl ketone\ the DakinÐWest reaction\ was _rst reported in 0817 and has been the subject of
considerable synthetic and mechanistic interest[ Early indications were that the reaction was limited
to amino acids with at least one a proton and the use of acetic anhydride to form methyl ketones
"Equation "76## but\ although yields may be highest under these circumstances\ this has now been
Bearin` a Nitro`en 070
LiO OLi O
H3 O+
N 71% N
BnO Li CO2Et BnO H CO2Et
Scheme 73
shown not to be the case[ Thus\ a broader range of alkyl ketones can be made using this method\
particularly as the most common acylating agents\ acid anhydrides\ are readily available[ The
conditions developed originally\ acetic anhydride at 099>C\ or 019>C for less reactive substrates\
were quite harsh\ but it has been demonstrated that the use of the acyl transfer catalyst 3!dimethyl!
aminopyridine dramatically reduces the reaction temperature ð77CSR80Ł[
O
The amination of ketone enolates is limited by the relative paucity of electrophilic aminating
agents\ although such species are known ð78CRV0836\ 80TL1248Ł[ Silyl enol ethers have been used in
conjunction with ethyl azidoformate "Equation "77## ð72TL482Ł or p!NO1PhSO1ONHCO1Et
ð83T2718Ł to introduce an N!ethoxycarbonyl amino group in reasonable yield and with azo!
dicarboxylates to give a!hydrazino ketones ð74SC538\ 83TL1316Ł[ The recent\ elegant work by Magnus
and co!workers on electrophilic addition to silyl enol ethers with double!bond transposition has
been extended to the synthesis of a!amino ketones "Equation "78##[ The p!toluenesulfonyl residue
can be removed without loss of the silyl group\ and the stereochemistry at the a position can be
inverted using an oxidationÐreduction sequence "Scheme 63#[ Perhaps the most unusual aspect of
the overall sequence is that the sulfonamide group is introduced initially into an axial position
ð89JA351Ł[
O-TMS O
EtOCON3, 110 °C, 15 h
NHCO2Et (88)
40%
Pri3SiO Pri3SiO
(p-TsN)2Se
NHTs
(89)
51%
Scheme 74
Scheme 75
O
+ ArCHO, (81) Ar
O N (90)
25–50% O N
S
OCONEt2
N + Cl–
Li
Bn
(80) (81)
This same connectivity can be achieved in the opposite sense by the addition of an a!nitrogen
anion to an acylating agent[ One obvious example involves the acylation of a nitronate anion "see
Section 2[93[6[1#\ although this requires an additional step involving reduction of the nitro group
to an amine[ There are\ however\ many ways in which nitrogen in a lower oxidation state can
stabilize adjacent anions\ although not all of these have been shown to react with acylating agents
ðB!76MI 293!97Ł[ Perhaps the most common approach involves the use of an amine substituted with
a cleavable\ electron!withdrawing group capable of coordination to\ and hence stabilization of\ an
adjacent anion "Scheme 65#[ This frequently means employing amides "e[g[\ "71##\ thioamides\ "e[g[\
"72## or formamidines "e[g[\ "73## ð65AG"E#202\ 79JA6014\ 70JOC3205\ 78JOC4540\ 78TL0086Ł[ The use
of formamidine!stabilized carbanions has been extensively exploited by Meyers and co!workers\
particularly for the synthesis of anions derived from cyclic amines ð74JOC0908\ 80JOC1640Ł[ Amino
methyl stannanes can act as amino alkyl anion equivalents without the need for strong base\
providing the electrophile is a highly reactive one such as an acid chloride[ Simple mixing of both
reagents\ in the absence of solvent for liquid acid halides\ gives tertiary a!amino ketones "Equation
"80##[ Aliphatic or aromatic acid chlorides behave as expected\ and formyl and nitrile groups remain
intact ð75TL1250Ł[ Additional anion stabilization can be provided by an adjacent conjugated
p!system[ Thus\ the dianion derived from ethyl N!benzoyl glycinate reacts from the a position with
acid anhydrides to give a!amido b!keto esters\ and decarboxylation proceeds smoothly to give
a!amino or amido ketones ð67CC642Ł[ Two complementary modes of reactivity are demonstrated by
the adduct "74#\ which is readily prepared by condensation of an aldehyde with an amino!substituted
phosphine oxide[ In the presence of base\ a conventional Wittig reaction gives the corresponding
enamine\ but\ in the presence of a proton source\ a thermal elimination of Ph1POH gives the amino
ketone ð70TL1688Ł[ A similar reaction occurs using a nitrile!stabilized carbanion[ Following addition
to an aldehyde\ elimination of HCN occurs regioselectively to give the desired product "Scheme 66#[
This route has excellent synthetic ~exibility\ relying\ as it does\ on readily available aldehyde and
Bearin` a Nitro`en 072
amine starting materials ð71TL528Ł[ The synthesis and reactions of nitrogen!stabilized carbanions
has been covered in a previous reviews ð73CRV360\ B!76MI 293!92Ł[
O S NR O OH
Et Me Me P
N N But N Ph R3
Et Ph
Et Me Me N
R1 R2
(82) (83) (84) (85)
X X Li
BunLi i, E+ E
R1 N R3 R1 N R3
ii, H3O+ R2HN R3
R2 R2
X = O, N, S
Scheme 76
O O
NEt2
Cl THF, 60 °C
+ Et2N SnBu3 (91)
84%
O O
O O
Scheme 77
Epoxides bearing a geminal leaving group have been used extensively for the preparation of
a!heterosubstituted ketones\ as the electron!de_cient substituent serves to activate nucleophilic attack
at the b position of the epoxide as well as providing the means for carbonyl group formation via a
0\0!elimination[ A number of substituents have acted in this way "Equation "81## ð89OPP288Ł\ of
which the most successful are the sul_nyl epoxides[ The substrates "e[g[\ "75## are easily prepared
using a Darzens type condensation of sul_nyl!stabilized carbanions with an aldehyde or ketone\
and the addition of a secondary amine gives good yields of the expected products "Equation "82##
ð75BCJ346\ 81SL344Ł[ 0\1!Disubstituted enamines react with sulfonyl oxaziridines to give a!amino
ketones via the possible intermediacy of a!amino epoxides[ For example\ the morpholine enamine
of cyclohexanone is converted into 1!morpholinocyclohexanone in 55) yield under mild reaction
conditions ð77TL3254Ł[
O
O
R2 R4XH R1 (92)
R1 R2
Z
XR4
Z = Hal, OR3, NO2, PhSO
O
O Ph
PhSO pyrrolidine
(93)
100% N
Ph
(86)
Despite their high reactivity as acylating agents\ acyl cyanides\ readily available from a carboxylic
acid derivative\ can be reduced to a!amino ketone hydrochlorides using SnCl1 ð61JOC207Ł or to
acetamido ketones "Equation "83## ð73TL1866Ł[ In the latter case\ isolated alkene\ ester or ketone
073 Dialkyl Ketones
groups survive\ although a\b!unsaturated acyl cyanides give mixtures of products[ Chemoselective
reduction of an a!nitro ketone to an a!amino ketone hydrochloride is possible using a poisoned
platinum catalyst ð75TL4648Ł[ Azides can also be reduced in the presence of ketones using catalytic
hydrogenation ð58CJC2378\ 74LA674Ł[ The Neber\ and mechanistically related\ rearrangements are
valuable routes to a!amino ketones which still _nd wide applicability owing to the ready availability
of the principal substrate\ O!tosyl oximes ð89OPP288\ 80COS"5#652Ł[ In fact\ any imine with an attached
leaving group will participate in the reaction\ and hence N!chloroimines and quaternary salts of
hydrazones behave in an analogous manner[ A common intermediate is an azirine "Scheme 67#
whose hydrolysis gives the desired products in which the carbonyl group is attached at the original
imine carbon[ For unsymmetrical imines\ the product arises from thermodynamic deprotonation
during the azirine!forming step[ Using anhydrous alcohols as solvents\ the amino ketals can be
formed instead of the ketones ð79S218Ł[ a!Halo imines can be used in an analogous manner "Scheme
67# ð71S654Ł[
O Ac2O, AcOH, Zn O
NHAc (94)
MeO2C CN 83% MeO2C
NOTs base N
R1 R2 R2
R1
R 4O –
H(R3) O
N H2O, HCl R1 R2
OR4
R1
R2 NH2(HR3)•HCl
R4O–
NR3
R1 R2
Hal
Scheme 78
The oxidation of 0\1!amino alcohols is an obvious method for the preparation of a!amino ketones\
although it can only be used for the formation of N!protected compounds^ otherwise\ side reactions
may cause a reduction in yield[ The other problem is the con_gurational instability of the products\
although this can be reduced by using N!phenyl~uorenyl ð76JA125Ł or N!TBDMS protecting groups
ð75TL3280Ł[ The alcohol oxidation can be done under Swern conditions ð75TL3280Ł\ with the CoreyÐ
Kim reagent ð77JA6336Ł or using chromium"VI# species ð89OPP288Ł[
2[93[6[0[1 b!Functionalized and more remotely NH1\ NHR and NR1!functionalized ketones
The importance of the Mannich reaction as a method for the formation of b!amino ketones is
enhanced by the biological activity of the products and also because of their value as intermediates
to a\b!unsaturated ketones and\ hence\ other multifunctional systems[ The immense amount of
literature in this area ð68T502\ 89T0680\ 80COS"1#782\ 80COS"1#842\ 80COS"1#0996Ł cannot be covered com!
prehensively in the space available here^ as a consequence\ only a brief summary of this reaction
and recent developments will be discussed[
The archetypal Mannich reaction consists of a three!component coupling between ammonia\ or
an amine\ a nonenolizable aldehyde and a carbon acid "pKa ³19#[ The optimum yields are obtained
using formaldehyde\ a ketone and a secondary amine "Equation "84## because primary amines
possess the ability to undergo dialkylation "Equation "85## and aldehydes as enolate donors tend to
undergo competing aldol reactions[ The former drawback can be overcome using additional\
temporary protection on the amine\ but the latter has been less successfully addressed[ Typical
conditions involve the use of an acid or\ occasionally\ base catalyst in a protic solvent where the
commonly accepted mechanism is as shown in Scheme 68[ Control of the regiochemistry of the
amino alkylation may be di.cult\ although the thermodynamic conditions mean that enolization
tends to occur towards the more!substituted a position "Equation 86#[ The main focus of recent
research has been directed towards the discovery of new methods that permit the use of the Mannich
Bearin` a Nitro`en 074
or related reactions in aprotic solvents\ without the use of acid or base catalysis or with increased
regioselectivity[
O
O CH2O, R2R3NH R1 R1
(95)
R1 R1
NR2R3
O O
O CH2O, R2NH2
R1 R1 (96)
R1 R1 N
R1 R2 R1
OH
R2 R2 + R1 R1
R2R3NH + CH2O N X N
R3 R3
O
R1 R1
NR2R3
X = OH, R2R3N
Scheme 79
O O O
Me2NH, CH2O
+ (97)
Me2N NMe2
1 : 3.5
One important component of this search has been the development of new procedures for the
formation of the intermediate aminal\ imine or iminium salt\ particularly those which allow for
the preformation or isolation of these reactive intermediates[ The simplest and most frequently
encountered Mannich reaction\ the introduction of a dimethylaminomethyl group as a means to
generate an a\b!unsaturated carbonyl compound\ is often done using the preformed iminium salts
"76# "XI\ Cl\ CF2CO1 or tri~ate "OTf## of which the _rst is the most familiar\ being Eschenmoser|s
salt[ The solubilities of these salts are very dependent on the counterion\ with the TFA and OTf
salts being most soluble\ particularly in less polar solvents where the use of these two reagents is
bene_cial ð68T502Ł[ The iminium salts can be prepared in a number of ways\ perhaps the most
common being one of the variations of the Bohme procedure in which N\N\N?\N?!tetra!
methylmethylenediamine undergoes elimination of dimethylamine promoted by TMS!I\ TMS!Cl or
AcCl[ However "77#\ "78# and many other compounds have been used to prepare similar iminium
species[
R1 R1
Me N N
+
N X– BunO NMe2
Me N
R1
(87) (88) (89)
As indicated above\ many Mannich reactions use a mixture of ketone\ formaldehyde and sec!
ondary amine\ although the frequent need for an acid or base catalyst and the regioselectivity
problems make this procedure far from general[ The use of preformed iminium salts "see above#\
which often work in the absence of a catalyst\ and the methodological advances that have been
made in the preparation of regioisomerically pure ketone enolates have enhanced the use of this
transformation[ The regioselective introduction of a dialkylaminomethyl group can be achieved
075 Dialkyl Ketones
using cyclic TMS enol ethers and Eschenmoser|s salt ð79TL794Ł or dialkylaminomethyl ethers
ð71TL436Ł[ Since these initial reports\ many other applications of the aminoalkylation of silyl enol
ethers have appeared\ demonstrating high levels of chemoselectivity ð80COS"1#782Ł[ Silyl dienyl ethers
may react preferentially from the g position "Equation "87## ð79TL794Ł\ while acyclic TBDMS enol
ethers undergo a synthetically useful amino methylation with double!bond inversion "Equation
"88## ð73TL4394Ł[ The low reactivity of these enol ethers and the related enol borinates is such that
useful yields can only generally be obtained with iminium salts[ Other than iminium salts\ a few
other species have been shown to act as e}ective partners in Mannich type reactions[ Imines or acyl
imines will react under some conditions\ but the reaction is often restricted to imines derived from
aryl or other nonenolizable aldehydes because of a competing isomerization of the imine to the
enamine ð83SC788Ł[ The more reactive N!acyl iminium salts will react with silyl enol ethers under
mild conditions to give the expected adducts in moderate diastereomeric excess "Equation "099##
ð89SL508Ł[
Me2NCH2•I
(98)
65%
O
TMS-O
NMe2
O-TBDMS O-TBDMS
Me2NCH2•I
(99)
NMe2
58%
O-TMS
OMe O Ph O O
TMS-OTf, –40 °C
N OBn (100)
61% Ph N OBn
Me Me
syn:anti 86:14
Two procedures have extended the Mannich reaction to the preparation of nonterminal b!amino
ketones by the use of aldehydes other than formaldehyde[ As indicated above\ this transformation
is very di.cult under classical Mannich conditions because of the self!condensation of enolisable
aldehydes[ Seebach and co!workers showed that aminoalkyl titanium alkoxides\ "89#\ prepared from
the corresponding aldehydes\ react directly with ketone enolates at low temperature "Scheme 79#
ð73HCA0482Ł[ In the second\ lithium enolates react with aminomethyl benzotriazoles to give amino
ketones[ This reaction is particularly useful for the preparation of highly hindered a\a!disubstituted
amino ketones "Equation "090## ð89T876Ł[
OLi
i, BunLi, –78 °C TiCl4, –70 °C
N
N ii, PrnCHO
H
OLi
OTiCl3 Prn O
N N
(90)
Scheme 80
Bearin` a Nitro`en 076
N
N OLi
O
N O
N + (101)
66% N
O
The development of the Mannich reaction as a method for the introduction of an NH1 or an RNH
group has not been particularly successful until comparatively recently[ Using the benzotriazole
methodology developed by Katritzky and co!workers\ however\ this can be achieved directly for
aromatic amines "Equation "091## or\ potentially\ from further derivatization of a secondary amide
"Equation "092## ð89T876Ł[ The imine "80#\ derived from formaldehyde and ammonia has been
generated\ in situ\ from TMS azidomethane and reacts with TMS enol ethers to give the expected
amines\ which could only be isolated following benzoylation "Scheme 70#[ Under otherwise identical
conditions\ 0\0\2\2!triisopropylsilyl "tips# enol ethers react with inversion of the double bond to give
compounds containing a primary amine "Equation "093## ð81JOC6998Ł[
N OLi O
N
N + PhHN (102)
85%
NHPh
N OLi O
N
N + BzHN (103)
85%
NHBz
O-TMS O
AlCl2R1 R3
i, R2 R3
TMS N3 + R1AlCl2 N R2
ii, BzCl
TMS
NHBz
(91)
Scheme 81
tips-O tips-O
(91)
NH2 (104)
94%
cis:trans 6:94
Although the transformation is not primarily aimed at the preparation of simple b!amino ketones\
brief mention must be made of the intramolecular Mannich reaction for the preparation of saturated
nitrogen heterocycles ð80COS"1#0996Ł[ A number of elegant syntheses have involved this reaction as
one of the key steps "Scheme 71# ð82JOC3551Ł[
The conjugate addition of nitrogen nucleophiles to electron!de_cient alkenes is a facile process
for which many procedures are available ð80COS"3#0Ł[ Benzophenone imine has been used as an
ammonia equivalent in the Michael addition to a\b!unsaturated carbonyl compounds[ Not sur!
prisingly\ perhaps\ with such a bulky nucleophile\ the addition is prevented by the presence of some
substituents at the b position of the enone ð78S248Ł[ For the addition of a dialkyl amine to exocyclic
a!methylene ketones\ a dramatic improvement was observed using aluminum oxide as a catalyst
ð79TL798Ł[ Using titanium"IV# amides in aprotic solvents\ one of the dialkyl amino groups is
delivered from the metal to the b position of an enone to give a titanium enolate which can undergo
further in situ aldol or Mukaiyama aldol reactions resulting in a b!amino b?!oxygenated ketones
ð80TL1260Ł[ b!Chloro ketones\ when accessible\ can act as surrogates for enones ð60JA1381Ł[
One problem with the Gabriel synthesis of amines is that the removal of the phthalimide group
requires relatively harsh conditions which may be incompatible with the presence of some other
077 Dialkyl Ketones
Ar
O–
Ar
BF3•Et2O, –20 °C aza-Cope
O
+
N
N H
Bn
H Bn
O– O Ar
H
Mannich
+
Ar
N 97% N
Bn H Bn
Scheme 82
functional groups\ and a number of modi_cations have been developed to address this "for a review
on the Gabriel reaction see ð80COS"5#54Ł#[ Among the ammonia equivalents which have been used
to prepare protected a! or b!amino ketones are the iminocarboxylates ð67JCS"P0#0977Ł\ dibenzylamine
ð80JOC346Ł and the sodium salts of tri~uoromethyl acetamide ð73S830Ł and the phosphoramidate
"81# ð71S811Ł[
O O
P
EtO N OBut
EtO Na
(92)
The reductive amination of aldehydes or ketones is often done using conditions where acid!
sensitive groups do not survive[ Using Ti"OPri#3 as a Lewis acid catalyst and NaBH2CN as the
reducing agent\ cyclic and acyclic acetals remain intact\ demonstrating the usefulness of this pro!
cedure for the synthesis of a wide range of carbonyl!protected amino ketones "Equation "094##
ð89JOC1441Ł[ 0\2!Diimines can be reduced to b!amino ketones ð72JOC1144Ł[
i, Ti(OPri)4
O ii, NaBH3CN O
O + N (105)
O N 50% O
H
The conjugate addition to enones of carbanions stabilized by an adjacent nitrogen atom has
recently been shown to be feasible\ although not without some problems[ Higher!order cyano!
cuprates derived from lithio formamidines undergo e}ective 0\3!addition "Equation 095#\ but
attempts to hydrolyse the formamidine lead to a mixture of products ð81TL4582Ł[ More successful
was the use of carbamate!stabilized anions\ generated by transmetallation "Equation 096#\ which
give good yields even with b\b!disubstituted ketones[ In some examples\ direct deprotonation of the
carbamate is e}ective\ and this obviously eliminates the requirement for formation of the stannyl
amine "Equation "097## ð82SL396Ł[ Unlike the formamidine protecting group\ the BOC group can
easily be removed[ Dianions derived from ethyl acetoacetate react with N!tosyl aziridines ð82SL653Ł[
O
O
Me CuCN, –78 °C
+ N SnBu3 (107)
BOC 64% Me
N
BOC
Bearin` a Nitro`en 078
O O
Me Me BusLi, TMEDA, CuCN, –78 °C
+ N Me (108)
BOC 63%
N
BOC
The reductive cleavage of the isoxazole ring was demonstrated many years ago to be a viable
method for the synthesis of b!amino ketones "Scheme 72# ð61JA8017Ł\ the isoxazole being prepared
from oxidation of the corresponding a\b!unsaturated oxime using iodine[ Now such ring systems
can be prepared from the 0\2!dipolar cycloaddition of nitrile oxides to acetylenes[ The regioselectivity
of the cycloaddition and the isolated yields of the adducts are often very high\ making the inter!
mediacy of isoxazoles one possible route to the preparation of b!amino ketones "for reviews on
0\2!dipolar cycloadditions see ðB!78MI 293!92\ 80COS"3#0958\ 80COS"3#0000Ł#[
R1 R2 R1 R2 R1 R2
Scheme 83
O
O OZnCl
LiHMDS, THF (93) 1 mol l–1 HCl
NHOH•HCl
Scheme 84
CHO HO
NHOBn
CH2NOBn, SmI2, ROH, HMPA
(109)
59%
089 Dialkyl Ketones
O O
NHOH
Cl
R2NO2S N
O
(93) (94)
O
OCO2Et
O O O
Pd(PPh3)4 Pd(PPh3)4
R2 R2 R1 R2 OH
70–80% 73–94%
O2N R1 NO2 O2N R1
Scheme 85
The conjugate addition of ButO1Li to b!nitro styrenes results in one of two products\ depending
on the substituents on the aromatic ring[ In the presence of electron!withdrawing groups the nitro
ketone is formed in good yield^ on the other hand\ for adjacent electron!donating groups the reaction
gives the nitro epoxide "Scheme 75#[ The latter pathway can be avoided by the addition of excess
base to accelerate deprotonation at the benzylic position ð77S118Ł[
The very strong anion!stabilizing properties of an NO1 group have a signi_cant impact on the
acidity of the adjacent protons "pKa ½09# and\ as a result\ there is an enormous body of literature
on the synthesis and reactions of anions adjacent to a nitro group[ Although alkylation of such
systems is di.cult\ they react with a\b!unsaturated ketones "0\3 addition#\ acid derivatives and
aldehydes[ C!Acylation adjacent to the nitro group is complicated by competing O!acylation\ but a
few acid derivatives have been used successfully\ including phenyl esters ð68S184Ł or\ more
commonly\ acyl imidazoles[ The latter can be used either with isolated lithium nitronate salts
ð71JOC3939Ł or with potassium or sodium salts generated in situ ð67S367\ 76S421Ł[ In a series of papers
Bearin` a Nitro`en 080
O
NO2
Ar
ButO 2 R
R BuLi, ButO2H NO2
Ar Ar 30–80%
NO2
R O
Ar
NO2
R
Scheme 86
Seebach and co!workers have demonstrated that the a\a!dianions of primary nitro compounds
demonstrate enhanced nucleophilic character with respect to the monoanions to the extent that
even simple esters act as e}ective C!acylating agents "Scheme 76# ð68HCA1147Ł[ The e.ciency of the
nitro group in charge delocalization is demonstrated by the fact that b!alkoxy groups\ as in "84#\ do
not undergo elimination during the deprotonation or subsequent acylation ð74JA2590Ł[
NO2
NO2 BuLi (2 equiv.)
NO2Li Me2CHCH2CO2Me
Li 70%
O
Scheme 87
O
O
NO2
O-THP
(95)
The coupling of nitronate anions to aldehydes to give 0\1!nitro alcohols\ the Henry nitroaldol
reaction\ is a facile process for which many experimental variations are known[ The products can
be oxidized to a!nitro ketones\ although elimination and retro aldol reactions may act as competing
pathways[ The optimum conditions appear to involve the use of chromium!based oxidants\ either
in the presence of a phase transfer catalyst ð73S596Ł or adsorbed onto a solid support ð75TL382Ł[
The synthesis and reactions of a!nitro ketones has been part of a recent review ð89OPP696Ł[
The formation of dianions from primary nitro compounds is complicated by the possibility of
generating two structural isomers[ Under Seebach|s conditions "Scheme 76# the a\a!dianion is
favoured and reacts with carbonyl!containing electrophiles to give 0\1!nitro alcohols[ However\ by
changing the concentration of HMPA and reversing the order of addition of the nitro alkane to the
base\ the a\b!dianion is preferred\ giving rise to 0\2!nitro alcohols "Equation "000## ð78CC009Ł[ Such
compounds could represent useful intermediates to b!nitro ketones\ but these can be prepared
directly from the addition of nitrite anions to a\b!unsaturated ketones or b!halo ketones ð70CL0566\
71CL72Ł[
OH
i, BunLi, THF, HMPA
OH
NO2 NO2 + (111)
Ph
ii, PhCHO Ph NO2
The other class of electrophile most frequently employed with nitronate anions are a\b!unsaturated
carbonyl compounds to give g!nitro ketones[ A wide variety of bases\ organic\ inorganic\ homo!
geneous and heterogeneous ð77S722Ł\ has been demonstrated to promote the addition\ although
competing side reactions\ such as polymerization of the intermediate enolate and the addition of
two molecules of enone to one of nitro alkane\ can reduce the yield in some cases[ One experimentally
simple procedure has been developed which requires no solvent and gives good yields of 0 ] 0 adducts
081 Dialkyl Ketones
"Equation "001##\ although it is susceptible to steric hindrance at the b position of the enone ð75S126Ł[
In a related reaction\ simple mixing of methyl vinyl ketone with nitromethane\ in water\ without
additional catalyst gives\ in quantitative yield\ a 3 ] 0 mixture of the adducts "85# and "86#[ There is
a strong rate enhancement of this reaction in the presence of sugars which has been attributed to
the hydrophobic e}ect ð81TL7962Ł[ The allylic anion derived from nitro alkenes adds from the
a!carbon to the b position of enones to give adducts like "87# ð76S147Ł[
O
NO2 O Al2O3, 5–8 h
O O + (112)
88% O O
NO2
O O O
O
O2N
NO2 NO2
(96) (97) (98)
g!Nitro ketones can also be obtained from the addition of enolate equivalents to nitro alkenes
ð75CRV640\ 76T702\ 81TL4530Ł[ The products are frequently required only as intermediates to
0\3!dicarbonyl compounds ð78CC730Ł\ obtained following a Nef reaction\ but can be isolated in
good yield[ For the reaction between substituted enolates and substituted nitro alkenes\ the diastereo!
selectivity of the addition has been extensively investigated ð74HCA051\ 89JOC0238Ł[ Variants of this
Michael addition which retain a nitro alkene in the product have been reported[ One proceeds via
exclusive SN1? addition to an allylic ester "Equation "002## ð74T3750Ł and the other via an additionÐ
elimination to a b!nitro enamine "Equation "003## ð76S618Ł[ This retention of the double bond allows
greater ~exibility in synthetic planning\ and in these two examples the position of the alkene is
complementary[ Chemoselective reduction of the nitro alkene in the presence of the ketone is
possible "Equation "004## ð77BCJ3918Ł[
OLi O
NO2 –78 °C to 0 °C
N NO2
+ (114)
O 55%
O O
NO2 Hantzsch ester NO2
(115)
90%
The preparation of a!keto oximes "a!hydroxyimino ketones# from ketones or from 0\1!diketones
is limited by the paucity of good electrophilic oxaminating agents or by regiochemical problems\
respectively[ Twenty years ago\ Hassner and co!workers demonstrated that silyl enol ethers react
with NOCl to give a!hydroxyimino ketones or a!nitroso ketones\ depending on the substitution
pattern at the a position "Scheme 77# ð63JOC1447Ł[ That a!nitroso ketones could not be isolated but
rapidly dimerized at room temperature was con_rmed later following the reaction between an enol
ether and methyl nitrite[ The dimers\ however\ are stable and could be isolated\ in some cases in
crystalline form[ Isomerization of the nitroso ketone dimers to the a!oximino ketones can be
achieved using acid\ base or heat ð68JOC164Ł[ Regiochemical control of the oxamination can also
be achieved using an in situ 0\3!reduction and enolate trapping procedure "Scheme 78# ð80BCJ1837Ł[
The reaction between a diazoalkane and an acid chloride to produce an a!diazo ketone is\ perhaps\
the best method for the preparation of such systems and one which has been widely used for many
Bearin` a Nitro`en 082
O O-TMS O
NOCl NOCl
R2 R2 R2
R1 R1 R1
R3 R2, R3 = alkyl, aryl R3 =H
NO R3 NOH
Scheme 88
NOH
O CoII, PhSiH3, BunONO OCoL2
O
67%
Scheme 89
years[ The reaction is most useful when using diazomethane to give terminal diazo ketones although
higher diazoalkanes have been used in some circumstances[ The diazotization of amino ketones is
rarely useful for the synthesis of a!diazo ketones\ except for a few speci_c examples\ but a more
general approach employs the Forster reaction "Equation "005##[ Some of the diazo ketones prepared
using these approaches can be found in the reviews ðB!75MI 293!94\ B!76MI 293!98\ 80COS"2#776Ł[ See
Chapter 2[01 for further discussion of diazo ketones[
O O
R1 chloramine R1 (116)
R2 R2
NOH N2
The diazotization of 0\2!dicarbonyl compounds with azides is a reaction which has been known
for many years and for which there are many experimental variations incorporating changes in the
azide used\ the solvent and the presence or absence of catalysts[ The relative safety of some of the
more common organic azides has been evaluated ð70SC836Ł\ but it is important to recognize that
any use of these reagents is potentially hazardous[ More recently\ 1!diazo!0\2!dicarbonyl compounds
have been prepared in the absence of solvent ð80SC080Ł\ using KF or K1CO2 as the base ð78SC1456\
89CC541\ 80S084Ł or with p!acetamidobenzenesulphonyl azide as the diazo source ð76SC0698Ł[ Two
diazotizing reagents which may be useful in speci_c cases are the phosphonium azide "88# ð89TL3876Ł\
which requires only a catalytic amount of base\ and the pyridinium salt "099#\ which works under
neutral conditions ð76SC872Ł[
N2+
N
+
P N N3
Et2N NEt2
NEt2 Et BF4–
(99) (100)
The diazotization of simple ketones is a less facile process owing to the reduced acidity of the
substrates\ but it can be achieved using mesyl azide ð75JOC3966Ł or arylsulphonyl azides in the
presence of phase transfer catalysts ð79S257Ł[ The former is attractive because of the lower cost\
although regioisomeric mixtures may result[ A more indirect route to the same products requires
temporary activation of the ketone with an electron!withdrawing group to direct diazotization
"Scheme 89# followed by in situ removal of the activating group ð57JOC2509\ 80SC080Ł[ A recently
reported version of this reaction involves regiospeci_c ketone tri~uoromethyl acylation prior to
diazo transfer "Scheme 80# ð89JOC0848Ł[ Possibly\ one of the many methods for regiospeci_c ketone
enolisation could be used to introduce the diazo group at either of the a!positions[
O O O
O
R1 R1 N2
R1 R2 R3
R2 R2
R3 = H, Ph
Scheme 90
083 Dialkyl Ketones
O i, LiTMP, –78 °C O O MeSO2N3
C5H11 C5H11
ii, CF3CO2Et CF3
O
O
C5H11
C5H11 N2 +
N2
9:1
LiTMP = lithium tetramethylpiperidide
Scheme 91
In the presence of an oxidizing agent\ azides react with dicarbonyl compounds to give di}erent
products[ For example\ using iodosobenzene\ 0\2!diketones undergo incorporation of azide at the
central position ð77T0592Ł[ In a more recent procedure\ Magnus and co!workers have disclosed a
useful a!azidonation of triisopropyl silyl enol ethers using NaN2 and cerium ammonium nitrate[
The isolated yields are good\ the reaction is regiospeci_c\ even for the thermodynamic enol silane
derived from 1!methylcyclohexanone\ and acetals and ethers survive the reaction conditions
ð81TL1666Ł[ In a highly unusual reaction from the same group\ triisopropyl silyl enol ethers react
with TMS azide and iodosobenzene to introduce azide regiospeci_cally at the b!position in high
yield "Equation "006##[ In this case\ the silyl group is retained during the oxidation ð81JA656Ł[
a!Azido ketones can be prepared from a!diazo ketones via the intermediate bromo ketones "Equation
"007## ð82CC83Ł\ and halo ketones in general react with NaN2 to give products arising from halide
displacement ð79TL820\ 75JOC2263\ B!77MI 293!94Ł[
O-tips O-tips
TMS-N3, PhIO
(117)
76% N3
O O O O
O i, HBr (1 equiv.) O
N2 ii, NaN3
N3
(118)
70%
NHZ NHZ
HO R2 S
R1 R3 O O
H
N SH carbodiimide NCS R2 = H
O NH
S NH R1 R1
R2 R3 R3
S R2
S R1 R3
Scheme 92
Bearin` a P\ As\ Sb or Bi 084
O O
N ArNCN
Ph3P R R
(101) (102)
NO i, BuLi, KOBut NO O
N N (119)
R1 Me ii, R2COCN R1 R2
Scheme 93
O
O
+
PMePri2
Ph
P(NEt2)2
(103) (105)
O R2PCl O
Bu3Sn R2P (120)
(104)
The use of phosphonium salts for the Wittig reaction explains the vast amount of literature
dealing with the synthesis of these species and their derived ylides[ Such a body of literature cannot
be covered comprehensively here\ but other recent reviews are available ð80COS"5#060\ B!83MI 293!90Ł[
The usual method for the preparation of b!keto phosphonium salts involves treatment of an a!halo
ketone with a phosphine "see the above reviews and ð76S0944\ 80T2236Ł#\ although the acylation of
ylides has also been reported ð77JOC4447Ł[ More remote keto phosphonium salts "e[g[\ "095# and
"096## can be prepared by the 0\3!addition of phosphines to enones ð80COS"5#060Ł or the addition of
085 Dialkyl Ketones
phosphines to cyclopropyl ketones ð76S537Ł[ Phosphonium salts "097# can be prepared from the
electrochemical oxidation of 0\2!diketones with PPh2 ð77CPB502Ł[
O O
O O
+
+ Ph3P R1 R2
Ph3P Ph +
PPh3
(106) (107) (108)
The chemistry of arsonium ylides has attracted recent attention owing to their ease of preparation
and the fact that their reaction with aldehydes or ketones can give alkenes with stabilized ylides or
epoxides with nonstabilized ylides[ For semistabilized ylides the outcome of the reaction depends
on other factors such as solvent\ base and the substituents on the arsine "for recent reviews see
ð76CSR34\ B!89MI 293!91Ł#[ Normally\ arsonium ylides are prepared by treatment of an alkyl halide
with an arsine ð69JOC1567\ 76TL1044\ 77S864Ł\ although for less reactive substrates a combination of
an alkyl tri~ate and a lithio diarylarsine may be more useful ð70JA0172Ł[ The arsonium salts and
their ylides are relatively easy to handle but the more volatile arsines should be treated with extreme
caution[ Arsenium ylides stabilized by two electron!withdrawing groups can be prepared from
1!diazo!0\2!dicarbonyl compounds and arsines ð71T2244Ł or 0\2!dicarbonyl compounds and arsine
oxides ð62T0586Ł\ and similar routes can be used for the preparation of stibonium ylides ð75T2776\
89TL4786Ł[
Ylides derived from bismuth and antimony are less well known than those derived from phos!
phorus and arsenic and are largely restricted to those derived from 0\2!dicarbonyl compounds[ The
_rst examples of bismuth and stibonium ylides were reported by Lloyd et al[ in the 0869|s and were
made by a thermal decomposition of a 0\2!diazo carbonyl compound in the presence of triaryl
bismuth or triaryl antimony species[ These two\ and arsenium ylides\ can be made using the same
procedure\ but at lower temperature\ by employing a copper catalyst ð77S208Ł[ An alternative
procedure for bismuth ylides has been developed using a b!diketone and a bismuth dichloride or a
bismuth oxide ð89BCJ849Ł[ This procedure has since been used to prepare one of the _rst examples
of a monocarbonylbismuth salt in very high yield "Equation "010## ð82TL7346Ł[ The chemistry of
arsenic\ antimony and bismuth compounds has been reviewed ðB!83MI 293!91Ł
TMS-O O
Ar3BiF2, BF3•Et2O
+
BiAr3 BF4– (121)
R 87–100% R
Scheme 94
O O O
(EtO)2PN(Bn)Pri
Br P (122)
Ph 50% Ph N(Bn)Pri
OEt
Bearin` a P\ As\ Sb or Bi 086
A number of methods which rely on a nucleophilic phosphorus species have been developed other
than the Arbuzov reaction[ Sodium diethyl phosphite reacts with a!halo ketones or 3!halo 0\2!
dicarbonyl compounds ð79TL1176\ 76TL234Ł to introduce a phosphonate group\ as in "098#\ and
trialkyl phosphite esters or dialkyl phosphite anions react with chloro or sulfonyl epoxides "Equation
"012## ð71CB590\ 82TL1036Ł[
O O
O SO2Ar NaPO(OEt)2
P (123)
82% EtO
EtO
O O O
P
EtO OEt
EtO
(109)
O i, Zn, CuBr O O
ii, RCOCl
P Br P (124)
EtO EtO R
EtO F 40–60% EtO F
F F
O O O O O O
P Bun4NBr, NaOH P piperidine, (CH2O)n P
OEt OEt OEt
OEt MeI OEt OEt
Scheme 95
Scheme 96
O O
P
EtO
EtO Cl
Cl
(110)
An alternative procedure has been developed by Oh and co!workers for the synthesis of b!keto
phosphonates having substitution at the a position[ Conjugate addition of organolithium reagents
to the silyl!substituted vinyl phosphonate "000# generates an intermediate anion which can be
acylated and desilylated in a one!pot procedure "Scheme 86# ð78TL2296Ł[ Another procedure starts
087 Dialkyl Ketones
with formyl phosphonates\ which can be converted into the corresponding enamines "Scheme 87#[
These enamines undergo kinetic deprotonation adjacent to the heterocycle to give an anion which
reacts with a range of electrophiles including alkyl\ allyl and benzyl halides and chloroformates
ð78TL3676Ł[ More conventionally\ perhaps\ the acid chlorides "001# react with a range of organo!
metallics to give the corresponding ketones ð75S550Ł[ Hydrolysis of b!keto phosphonates to b!keto
phosphonic acids can be done with TMS!Br ð78JMC0775Ł[
O
PO(OEt)2 i, PhCOCl
PO(OEt)2 ButLi, –78 °C ii, H3O+ (EtO)2OP
But Ph
TMS TMS 73%
Li
(111) But
Scheme 97
O i, BunLi, –78 °C, THF then DMF O i, BunLi, –78 °C, THF then MeI
ii, pyrrolidine, C6H6, reflux ii, H3O+
P R P
EtO EtO N
EtO
60–70% EtO 70–80%
R
O O
P
EtO
EtO
R
Scheme 98
O O
P
EtO Cl
EtO
R
(112)
Wiemer and co!workers have developed several procedures for the synthesis of b!keto phos!
phonates using electrophilic phosphorus species[ In one of their early publications\ a!bromo ketones
were converted into dilithium reagents which react with chloro phosphates as shown in Scheme 88[
The phosphonates "002# and "003#\ which cannot be made by conventional Arbuzov chemistry
owing to competing elimination in the bromo ketone or the low nucleophilicity of an electron!
de_cient ~uorinated phosphine\ respectively\ can be made in 51) and 39) yields using this
approach ð75JOC3231Ł[ A modi_cation of this procedure was reported subsequently in which
O!phosphorylation of anenolate anion was followed by a base!promoted 0\2!shift of the phosphonate
group[ This migration occurs without the need for potentially hazardous ButLi and in higher yield
"Scheme 099^ cf[ Scheme 88#[ Unfortunately\ this procedure does not work for acyclic ketones or
for cyclic ones larger than cyclohexanone[ For ketones with more than one set of a protons\ a
mixture of products may be obtained "Equation "014##\ suggesting\ in these cases\ the intermediacy
of an allylic anion[ However\ in cases where the steric environment at the two a positions is
signi_cantly di}erent\ the reaction may still be synthetically useful "Equation "015## ð75TL3154\
76JOC3074Ł[ Cyclohexadienyl phosphates\ prepared as shown in Scheme 090\ also undergo a regio!
speci_c migration arising from removal of the proton at the terminal position of the diene ð89JOC1731\
81JOC206Ł[ Tertiary b!keto phosphonates\ which may not be generally available using the methods
outlined above\ can be prepared from a!hydroxy ketones and diethyl chlorophosphite "Equation
"016##[ The reaction may proceed via the intermediate mixed phosphite ester ð78JOC516Ł[ Perhaps
the most intriguing method developed by this group involves the C!phosphitidation of ketone
enolates followed by air oxidation to the phosphonate "Scheme 091#[ Unlike some of the methods
described earlier\ this route is applicable to the synthesis of medium! and large!ring keto
phosphonates and acyclic ones\ and it has been used on a scale up to 9[0 mol ð80JOC4445Ł[ This
method was independently investigated by another group who used H1O1 as the oxidant
ð80TL1470Ł[
Bearin` a P\ As\ Sb or Bi 088
Scheme 99
Scheme 100
OPO(OEt)2 O O
LDA (EtO)2OP PO(OEt)2
+ (125)
D D D
1:1
OPO(OEt)2 O
LDA (EtO)2OP
(126)
80%
O OPO(OEt)2 O
i, LDA LDA (EtO)2OP
ii, ClPO(OEt)2 58%
Scheme 101
O O
(EtO)2PCl, FeCl3
(127)
OR PO(OEt)2
R = H, 96%
R = Et3Si, 67%
O OLi i, ClP(OEt)2 O
LDA, Et2O, HMPA ii, air or O2
R1 R1 R1 PO(OEt)2
44–80%
R2 R2 R2
Scheme 102
O O O O
P P
Ph OEt Ph OCH2CF3
OEt OCH2CF3
(113) (114)
199 Dialkyl Ketones
Two complementary procedures have been developed for the synthesis of b!keto phosphonates
or phosphine oxides using diazo compounds[ In the _rst\ 1!diazo ketones or 1!diazo 0\2!diketones
react directly with dialkyl hydrogenphosphite in the presence of a copper catalyst ð89S404Ł^ in the
second\ aldehydes insert into diazo phosphonates or phosphine oxides to give identical products
using SnCl1 as the catalyst "Equation "017## ð81TL0020Ł[ Nucleophilic addition of ethoxide to the
allenic phosphonate "004# occurs at the central carbon atom of the allene to give an enol ether which
can be hydrolysed to a b!keto phosphonate ð71AG"E#260Ł[ Allene oxides "005#\ which can be prepared
in enantiomerically pure form\ react with water as shown in Equation "018# ð82TL7432Ł\ and
hydroxy!substituted keto phosphonates can also be prepared using a 0\2!dipolar cycloaddition
"Equation "029## ð76BCJ1352Ł[ The hydration of alkynes is a well!known method for the synthesis
of ketones\ and the presence of a phosphonate group on the alkyne does not appear to prevent the
reaction from occurring as expected "Equation "020## ð76JOC3709Ł[
O O
SnCl2
P N2 + Ph (128)
Ph CHO POPh2
53% Ph
Ph
O PO(OEt)2
O •
C5H11
(115)
O O
H2O
Bun PO(OR)2 (129)
Bun
74%
PO(OR)2 OH
(116)
i, CO2Me
ii, Raney Ni O OH
(EtO)2OP
+
(EtO)2OP (130)
N O– 52% CO2Me
O O
HgSO4, H2SO4
PO(OEt)2 (131)
98%
PO(OEt)2 O
O
Ph O-TMS O
Ph P O
PO(OEt)H Ph
OEt P H(HO)OP
OEt
(117) (118) (119) (120)
O i, 2-hexen-4-one
O-TMS i, 1-hexen-3-one ii, H3O+
O-TMS
P Prn P
H O-TMS ii, HMDS 83%
O-TMS
(121)
O O
O
Prn P Et
OH
HMDS = hexamethyldisilazide
Scheme 104
O
O
O OEt
P OEt PO(OEt)2
PO(OMe)2 OEt
OH
R
PhCHCHCOMe
(EtO)2OP
R = H, 88%
Ph O
M
(EtO)2OP
R
(125) i, PrnCHC(Et)NO2 R O
ii, O3 (EtO)2OP
R = H, 70%
Prn
Scheme 105
191 Dialkyl Ketones
2[93[8 KETONES BEARING A METALLOID FUNCTION
TMS TMS
RhH(PPh3)4
(132)
Ph 56% Ph
HO O
HO OH TFA
O TBDMS
TBDMS (133)
Prn Prn 90% Prn Prn
i, TMS-Cl
i, MeLi ii, TFA
OAc OLi O
ii, ButLi 64%
Br Li TMS
Scheme 106
MgBr2 O
n-C9H19CHO + TMS-CHN2 TMS (134)
57% n-C9H19
i, activated Mg O
n-C5H11 SiMe2Ph ii, CuBr•Me2S
n-C5H11 (136)
n-C7H15
Cl iii, n-C7H15COCl
SiMe2Ph
But But
>95 : <5
O O
O B , LDA
Cl O
B O (140)
83%
O
SnMe3
O
SnMe3
de > 98%, ee, > 96%
Scheme 107
Copyright # 1995, Elsevier Ltd. All R ights Reserved Comprehensive Organic Functional Group Transformations
3.05
Ketones: a,b-Unsaturated Ketones
WARREN J. EBENEZER and PAUL WIGHT
ZENECA Specialties, Manchester, UK
2[94[0 KETONES BEARING AN a\b!ALKENIC BOND 195
2[94[0[0 a\b!Unsaturated Ketones without Further Unsaturation 195
2[94[0[0[0 From diazo ketones 195
2[94[0[0[1 By elimination reactions 195
2[94[0[0[2 From vinyl compounds and carboxylic acid halides or their equivalents 109
2[94[0[0[3 From a\b!unsaturated acid chlorides or their equivalents and carbon nucleophiles 101
2[94[0[0[4 From alkylations of a!b!unsaturated aldehydes and their equivalents 102
2[94[0[0[5 By oxidation reactions 104
2[94[0[0[6 Rearran`ement reactions 105
2[94[0[0[7 By displacements of a b!leavin` `roup on an a\b!unsaturated ketone 106
2[94[0[0[8 OxyÐCope and Claisen rearran`ements 106
2[94[0[0[09 Carbonylation and related reactions 107
2[94[0[0[00 By isomerisations 107
2[94[0[0[01 By aldol condensation reactions 108
2[94[0[0[02 By Witti` reactions 119
2[94[0[0[03 By DielsÐAlder reactions 110
2[94[0[0[04 By oxidations of furans 110
2[94[0[0[05 From alkynes 111
2[94[0[0[06 From cyclopropanes 113
2[94[0[0[07 By ð2¦1Ł cycloaddition reactions 114
2[94[0[0[08 Miscellaneous reactions 114
2[94[0[1 a\b!Unsaturated Ketones with Further Unsaturation 114
2[94[0[1[0 By elimination reactions 114
2[94[0[1[1 By displacement reactions of a b!leavin` `roup with a vinyl nucleophile 117
2[94[0[1[2 By isomerisations of double and triple bonds 118
2[94[0[1[3 From oxidations of further unsaturated allylic alcohols 118
2[94[0[1[4 From reactions of further unsaturated a\b!unsaturated acids and their equivalents with
carbon nucleophiles 118
2[94[0[1[5 By FriedelÐCrafts acylations of dienes 129
2[94[0[1[6 a!Allenic ketones 129
2[94[0[1[7 By aldol condensation reactions 129
2[94[0[1[8 By Witti` reactions 120
2[94[0[1[09 From pyrilium salts 121
2[94[0[1[00 From cyclopropanes 121
2[94[0[1[01 By Claisen rearran`ements 122
2[94[0[1[02 Carbonylation reactions 122
2[94[0[1[03 Miscellaneous methods 122
2[94[0[2 Halo`enated a\b!Unsaturated Ketones 123
2[94[0[2[0 1!Halo`enated a\b!unsaturated ketones 123
2[94[0[2[1 2!Halo`enated a\b!unsaturated ketones 127
2[94[0[3 Oxy`en!substituted a\b!Unsaturated Ketones 139
2[94[0[3[0 1!Oxy`en!substituted a\b!unsaturated ketones 139
2[94[0[3[1 2!Oxy`en!substituted a\b!unsaturated ketones 132
2[94[0[4 a\b!Alkenic Ketones with Sulfur!based Substituents 136
2[94[0[4[0 1!Thio a\b!unsaturated ketones 136
2[94[0[4[1 2!Thio a\b!unsaturated ketones 140
2[94[0[5 Selenium! and Tellurium!substituted a\b!Unsaturated Ketones 145
2[94[0[6 a\b!Alkenic Ketones with Nitro`en!based Substituents 146
2[94[0[6[0 1!Nitro`en!substituted a\b!unsaturated ketones 146
2[94[0[6[1 2!Nitro`en!substituted a\b!unsaturated ketones 150
194
195 a\b!Unsaturated Ketones
2[94[0[7 Phosphorus! and Arsenic!substituted a\b!Unsaturated Ketones 158
2[94[0[8 a\b!Alkenic Ketones with Silicon!based Substituents 169
2[94[0[8[0 1!Silyl a\b!unsaturated ketones 169
2[94[0[8[1 2!Silyl a\b!unsaturated ketones 160
2[94[0[09 a\b!Alkenic Ketones with Metal Substituents 161
O
O
Cu(acac)2, 60 °C
N2 (1)
N2 O
70%
O
(E):(Z) 10:1
O BF3•OEt2, 0 °C
(2)
65%
O
N2
O-TMS O
Pd(OAc)2, 25 °C
(4)
94%
(E)
O H CO2Me O H CO2Me
i, TMS-Cl, Et3N, DMF, 130 °C
ii, Pd(OAc)2, 20 °C
(5)
55%
H H
O-TMS O
Ph3C+ BF4–, 25 °C
(6)
70%
O O
i, LDA, PhSeBr
ii, H2O2
(7)
72%
O-TMS O
i, PhSeCl
ii, mcpba
(8)
CO2Me 51% CO2Me
i, PhSeCl, EtOAc
O ii, H2O2 O
(9)
64%
197 a\b!Unsaturated Ketones
O O O O
i–iv
(10)
62%
HMPA = hexamethylphosphoramide
O i, Br2, CH2Cl2
O
ii, MgO, DMF, 140 °C
(11)
96%
O i–iv O
(12)
67%
OH
i, HO , p-TSA; ii, Br2; iii, KOH, DMSO; iv, p-TSA, H2O
i, NaH, THF
ii, Br2
iii, LiCl, DMF
(13)
O 70%
H O
MeO2C
O i, SO2Cl2, CCl4 O
ii, LiBr, Li2CO3, DMF, 153 °C
(14)
76%
O O
i, PhNMe3+ Br3–
ii, pyridine
(15)
77%
Ph O
H Ph O
Br HBr, 118 °C
(16)
55%
H
a\b!Alkenic Bond 198
OMe O
HO i, POCl3, pyridine
ii, H+
(17)
64%
i, LDA
O O
ii, MeSSMe
iii, NaIO4, 120 °C
(18)
79%
O O
MeO MeO
NaH, PhSO3Me, DME, ∆
(19)
Ph Ph
O O i, LDA S –O S
ii, CaCO3, 150 °C O O
+ Ph S O
+
62%
Cl
Ph
S
O
O
Scheme 1
O-TMS
H3PO4 O
O-TMS (21)
73%
O Me O
O
S N LDA, THF S
Ph Ph Ph (23)
77%
OH O
H H
O O
Pb(OAc)4, Cu(OAc)2, pyridine
(24)
89%
H H
CO2H
i, Me2NH•HCl
O ii, MeI O
iii, DMF, 75 °C
CO2Me + HCHO (25)
n-C6H13 n-C6H13
52%
2[94[0[0[2 From vinyl compounds and carboxylic acid halides or their equivalents
O O
MgBr THF, Et2O
+ OEt OEt (27)
EtO
87%
O O
MgBr
O Pd(PPh3)4, Et2O O
+ (28)
But Cl 82%
But
O
O
Me AlMe2 Cl, AlCl3
CpZr + (29)
Cl 61%
N Li O
2
(30)
O 45%
TMS O
O AlCl3, CH2Cl2, 0 °C
+ (31)
Cl 77%
COCl O
AlCl3, CH2Cl2
(32)
95%
TMS
i, LiOH H
ii, (COCl)2, DMF
iii, EtAlCl2
(35)
MeO2C
72% O
H
MeO2C MeO2C
O
ClOC COCl
AlCl3, MeNO2
(36)
51%
O
O
i, P2O5
O ii, K2CO3
O (37)
94%
O
H3PO4, 110 °C
CO2H (38)
87%
2[94[0[0[3 From a\b!unsaturated acid chlorides or their equivalents and carbon nucleophiles
O
O
CO2Et LDA
Me + (39)
N CO2Et
58%
OMe MeO OMe
MeO OMe
a\b!Alkenic Bond 102
O BF3•OEt2, BusLi N
+ (40)
OMe N 69%
Me
O
O O
OMe MeMgCl
N (41)
Me 79%
N N
Me Me
O
O 20 °C
+ (42)
O O-TMS 80%
Cl
O O
O O
AlCl3
+ (43)
Cl TMS 90%
i, LDA
ii, BunBr
O-TMS iii, Et3N, HF, NaOH O
(44)
CN 54%
i, BuLi O O-TMS
O O ii, Ti(OPri)4
iii, aldehyde
O NPri2 + (45)
62% O NPri2
SO2Tol O-TMS
O
(1)
103 a\b!Unsaturated Ketones
Cl
O
O CN NaN(TMS)2
(46)
50%
Corey has used the dithiane "1# which can be alkylated predominantly at the sulfur!substituted
carbon "Equation "36## ð64TL814Ł[ Similarly the anion of "2# is alkylated adjacent to the cyano group
"Equation "37## ð75CB611Ł^ see also ð62AG"E#58\ 73TL1474Ł[ Seebach has shown that the dithiane "3#
can act as a formyl dianion equivalent\ and can be alkylated with two di}erent electrophiles
"Equation "38## ð63TL2060Ł[ a\b!Unsaturated aldehydes can also be umpoled with a metal catalyst
such as CoCl1\ which is believed to proceed via a radical mechanism "Equation "49## ð77CC581Ł^ see
also ð77JOM"237#012\ 89JOC1443Ł for use of Ni"cod#1 in the addition a\b!unsaturated aldehydes to
alkynes[ A further aldehyde umpolung strategy is to use an allenyl ether\ which can be a!metallated
and alkylated[ Hydrolysis then gives the a\b!unsaturated ketone "Equation "40## ð62TL1474Ł[
Hegedus and co!workers have developed a palladium!catalysed version of this transformation\
which can be used to give divinyl ketones[ The reaction proceeds with retention of con_guration
"Equation "41## ð72JA832Ł[ Parsons has described a similar reaction using an allenyl thioether
ð67CC711Ł[
i, LDA O
S S ii, MeI
iii, HgCl2
(47)
74%
(2)
i, LDA
ii, MeI O
CN iii, Et3N•HF
(48)
O-TMS 59%
(3)
Li TMS I
O
O i, BuLi, HMPA
S S + + (49)
ii, NH2OH
(4)
O
O O O CoCl2, MeCN
+ (50)
O 89%
O
OMe O
i, BunLi, MeI
ii, H+
• (51)
100%
n-C5H11 n-C5H11
OH H2Ru(PPh3)4 O
(54)
95%
OH OH K2FeO4 O OH
(55)
Ph 95% Ph
[O]
R
R (56)
O
CrO3•pyridine
OMe (57)
O 58% OMe
O
O
O
O
CO2Me ButO2H, Cr(CO)6 (cat.) CO2Me (58)
83%
OH O
O
R3 HO
R3
R3
R2
R2 R2
R1
R1 R1
Scheme 2
O
50 °C
+ • (61)
90%
•
O
O O
mcpba, 150 °C
+ • (62)
45%
PhS
(5)
a\b!Alkenic Bond 106
O
O
+ OAc (63)
80% Cl
Cl3C Cl
AcO Cl
i, TFAA, collidine O
NMe2 ii, NaOH, 41 °C
+ But (64)
O 69%
But
TFAA = trifluoroacetic anhydride
O O
ButCuLiSPh
(65)
70%
Br But
i, ClPO(OEt)2
O O ii, Me2CuLi O
(66)
83%
MeO
O
170 °C
(68)
62% O OMe
O
HO
107 a\b!Unsaturated Ketones
KH, 18-crown-6, 25 °C
OH (69)
75%
O
O
O toluene, 180 °C
(70)
60%
O-TBDMS O-TBDMS
i, Co2(CO)8
ii, sealed tube, CO, 85 °C
O (71)
64%
MOM-O MOM-O H
O OMe
CO2Et
Br CO2Et Bun3Sn CO, 50 °C, Pd(dba)2
+ (72)
OMe O-THP 74%
O-THP
2[94[0[0[00 By isomerisations
A common method of forming a\b!unsaturated ketones is to isomerise a b\g! or g\d!unsaturated
ketone to the more thermodynamically stable conjugated isomer[ These isomerisations occur most
readily with base catalysis often in very high yield ð59JOC0855\ 75JA1989\ 78TL6186Ł[ Acid catalysis has
also been reported ð42JA2157Ł as has thermal isomerisation ð75HCA117Ł and the use of rhodium
compounds which can be tuned to give either the more or less substituted enone where a choice is
available ð68TL0388Ł[ Oxidations of homoallylic alcohols can result in concomitant isomerisation to
the unsaturated ketone ð45JA765\ 76TL2004Ł[ Birch reductions of phenol derivatives are commonly
followed by isomerisation to the more stable cyclohexenone in situ or on acidic workup ð67CC741\
68BSF270Ł[
a\b!Alkenic Bond 108
2[94[0[0[01 By aldol condensation reactions
Probably the most important and versatile route to a\b!unsaturated ketones is the aldol conden!
sation[ This involves the reaction of an enolate or enol with an activated carbonyl\ followed by
dehydration or similar elimination of the resulting adduct[ Thus\ reaction of the 0\2!diketone "5#
with dichloroaldehyde "6# followed by elimination of acetic acid gives the ketone "7# in 66) yield
"Equation "62## ð70JOC2115Ł[ Aldol reactions are often carried out in situ after the removal of a
carbonyl protecting group and occur with both acid and base catalysis "Equations "63# and "64##
ð70JA2359\ 73JOC299Ł^ see also ð64JA5800\ 67TL1844\ 79JOC3491\ 70JOC1317\ 74CL0034\ 76JHC386Ł[ Similarly\
functionality can be manipulated to give a dicarbonyl compound which undergoes an intramolecular
aldol condensation leading to a cyclic unsaturated ketone[ Thus\ opening the lactone "8# with a
Grignard reagent gives a 0\4!diketone which cyclises under basic conditions to give the cyclo!
hexenone "09# in the FujimotoÐBelleau reaction "Equation "65## ð78JOC3691Ł^ see also ð54JCS0245\
71CJC1417Ł[ Another method of unmasking dicarbonyl functionality is to ozonise an alkene\
especially a cyclic alkene "Equation "66## ð60JA3221\ 71SC884\ 80TL4586Ł[ Other oxidations leading to
precursor dicarbonyl systems are known ð72JA4577\ 75NJC456Ł[ Reductions leading to dicarbonyl
systems have been reviewed ð78JOC3562Ł as have reductions of heteroaromatic ring systems "e[g
Equation "67## ð64JA279\ 71TL4998\ 89JOC1126Ł[
Cl O
O O K2CO3, THF, 67 °C
+ OHC Cl Cl (73)
77% Cl
(6) (7) (8)
MeO2C
p-TsOH, toluene, 130 °C O
(74)
MeO O 51%
O
MeO O
O
i, 1N HCl O
O
ii, 1N NaOH, 100 °C
N (75)
50%
N
O O
O
i, O3
ii, Me2S or Zn
iii, PhCH2NMe3Cl, 50% NaOH, CH2Cl2
(77)
38%
i, Na, NH3
ii, NaOH, EtOH (aq.)
O O iii, H3O+
O (78)
52%
N
O
119 a\b!Unsaturated Ketones
The aldol reaction can be made regioselective by preparing an enol derivative of the ketone\ in
order to ensure that coupling occurs on the desired side of an unsymmetrical ketone[ A number of
preformed enolates have been used\ the most common being the silyl enol ether which is reacted
with the aldehyde or ketone in the presence of a Lewis acid catalyst\ for example TiCl3 ð66AG"E#706Ł[
Silyl enol ethers also react with acetals in the presence of a stoichiometric amount of TiCl3 to
provide Aldol products in high yield ð76S0932Ł[ This reaction\ known as the MukaiyamaÐaldol
condensation\ has become an important synthetic tool facilitating aldol condensations which do
not proceed under conventional conditions "Equation "68## ð67TL3194\ 78JA7166Ł^ see also ð71TL0936\
73JOC2593Ł[ Enamines are also commonly used as preformed enolates ð51CB0384\ 70S088Ł[ Another
important aldol reaction leading to unsaturated cyclic ketones is the Robinson annulation reaction
in which a cyclic ketone is treated with methyl vinyl ketone "or a derivative# under basic conditions
ð65S666Ł[ Another annulation procedure for cyclic ketones has been reviewed ð76JOC0339Ł "Equation
"79## and other variants are known ð64JOC2510\ 66S597\ 67JA5183\ 67JOC3549\ 89S882\ 89TL5034Ł[
O
TMS-O
TiCl4, 0 °C
O (79)
60%
O
i, LDA, THF
O ii, (Ph3P)4Pd
iii, NaOH, EtOH (aq.)
+ Cl O (80)
OP(O)(OEt)2 79%
O O
P(OR2)2
R1
(11)
a\b!Alkenic Bond 110
O
O NaH, THF CO2Et
Ph3P CO2Et
+ OHC (82)
38%
O THF, –78 °C
+ (MeO)2P Li (83)
37%
O
O O
O S
LDA, –5 °C S S
+
+ Ph3P O (84)
S 55%
O
–
+
• O
Ph3P
(12)
O
O i, xylene, 140 °C
MeO H SO2Ph
ii, H+
+ (85)
O-TMS 69%
SO2Ph
O
MeAlCl2
O
H O O
H O , DCE, 70 °C
O
(86)
89%
H ( )7 ( )7
H
HO2C HO2C
DCE = 1,2-dichloroethane
pcc, DCM, 20 °C
SMe (87)
O SMe 70% O O
pcc = pyridinium chlorochromate
DCM = dichloromethane
OH
O O-MOM O O-MOM
i, Me2CuLi
(89)
ii, PriSLi
O ZnI2
CH2Cl2, 20 °C
+ O + O (90)
64%
3:1
CuLi
Et2O, THF, –40 °C 20% HCl
Bun CuLi + 2 X Bun 2
2
75% overall
X
(13) X = SR, OR (14)
Bun
Scheme 3
a\b!Alkenic Bond 112
The reduction of a!alkynic ketones similarly leads to a\b!unsaturated ketones "Equation "80##
ð68CL0910\ 75S073Ł[ In general catalytic partial hydrogenation leads exclusively or predominantly to
"Z#!alkenes\ whereas reduction with metals and metal salts gives predominantly "E#!alkenes ðB!73MI
294!90Ł^ for a comprehensive list of reagents and references see ðB!78MI 294!90Ł[
O
CrSO4, DMF, H2O, 25 °C O
(91)
80%
The synthetically useful reaction of trialkylboranes with a!alkynic ketones occurs only in the
presence of catalytic amounts of oxygen and yields the a\b!unsaturated ketone\ as a mixture of
stereoisomers\ after hydrolysis of the intermediate allene "Equation "81## ð69JA2492Ł[ A multistage
synthetic procedure to 2\2!dimethyl unsaturated ketones has been reported which involves the
anionotropic rearrangement of 0!halodienylboranes with sodium methoxide followed by oxidation
and isomerisation "Scheme 3# ð77S029Ł^ see also ð62CC595Ł[
air O
O
THF, H2O, 20 °C
B + (92)
3
65%
I R
NaOMe, MeOH i, H2O2, NaOH (aq.), THF O
B B ii, ButOK, ButOH R
R OMe
Scheme 4
Dreiding has reported that the pyrolysis of a!alkynic ketones leads to fused and spiro!cyclo!
pentenone systems\ via an alkylidene carbene intermediate\ in high yield enabling a total synthesis
of the triquinane modhephene "Equation "82## ð70HCA0012\ 74HCA227Ł[ Radical chemistry also
enables the synthesis of a\b!unsaturated ketones from a!alkynic ketones[ Thus a radical cyclisation
followed by protiodestannylation provides a neat synthesis of a!methylenecyclohexenones "Equation
"83## ð89TL4928Ł^ also see ð89JA891Ł[ Electrophilic alkylation of an allenic anion\ derived by metal!
lation of the silyl alcohol "04# also leads to a\b!unsaturated ketones in high yield "Equation "84##
ð79TL512Ł[
620 °C
(93)
95%
O O
AIBN = 2,2'-azobisisobutyronitrile
HO TMS O
i, BunLi
Ph (95)
ii, MeI Ph
(15)
113 a\b!Unsaturated Ketones
2[94[0[0[06 From cyclopropanes
Cyclopropanes have proved useful intermediates in the synthesis of a\b!unsaturated ketones via
ring cleavage reactions[ Thus\ Conia et al[ have reported that the cycloadditions of chloro!
methylcarbene to the trimethylsilyl enol ethers of cyclic and acyclic ketones\ followed by elimination
of TMS!Cl with ring opening of the cyclopropane\ leads to a!methylalkenones "ring expanded by
one carbon atom in the case of cyclic ketones# "Equation "85## ð70S178\ 70S180Ł^ see also ð63TL898\
63TL2186Ł[ A similar overall result is achieved by the reaction of a!haloketones with dilithio!
alkylsulfones via a cyclopropane intermediate "Equation "86## ð74JOC2563Ł[ The acidic hydrolysis of
dichlorocyclopropylcarbinols such as "05# leads to cyclic enone systems in good yield[ This reaction
has been postulated to occur via conjugate dehydration\ Nazarov!type cyclisation and hydrolysis
of the resulting chlorodiene "Equation "87## ð63JA2602Ł\ and it is also applicable to forming bicyclic
systems ð67TL660\ 79BCJ0909Ł[
Cl
O
toluene, 111 °C, 6 d
(96)
TMS-O
91%
O O
Li THF, 0 °C
Cl
+ PhSO2 (97)
Li 45%
Cl Cl O
HBr (aq.), 100 °C
OH (98)
83%
(16)
Ring opening reactions of oxycyclopropane systems derived from the reaction of a!diazocarbonyl
intermediates with enol ethers or enol acetates lead to 0\3!dicarbonyl functionality which can then
undergo Aldol cyclisations leading to cyclic enones "Equation "88## ð60TL1464\ 67JA0156\ 89CB252Ł[
The ring opening of other oxycyclopropane systems has been widely used in synthesis[ Base!
catalysed cleavage of 0!siloxy!1!vinylcyclopropane leads to an a!methylenone function ð62TL1656Ł^
see also ð62JOC293Ł[ Treatment of bicyclic cyclopropanes such as "06# with FeCl2 followed by sodium
acetate results in cleavage of the bridging bond to give the cyclic enone "07#\ possibly via a radical
mechanism "Equation "099## ð65JOC1962\ 79OS"48#002\ 77CL810\ 82TL6180Ł[ By contrast treatment with
TeCl3 followed by dimethylsulfoxide provides the corresponding a!methylene in good yields via an
intermediate b!trichlorotelluro ketone ð80TL118Ł[
O
O
NaOH, MeOH, 100 °C, 1 h
OAc (99)
85%
(17) (18)
The ring opening of cyclopropylphenyl sul_des has also been used synthetically to make
a\b!unsaturated ketones[ Thus the alcohol "08#\ prepared from the addition of 0!lithiocyclo!
propylphenyl sul_de to 3!methyl!0\1!epoxypentane\ has been cleaved\ hydrolysed and dehydrated
in a single pot using mercuric chloride\ to a}ord the enone "19# "Equation "090## ð71TL1268Ł[
a\b!Alkenic Bond 114
SPh
O
(19) (20)
O
Zn
Et2O 2
MOM-O CuI, HMPA, 25 °C
CO2Et
CO2Et (103)
C5H11 71%
C5H11
MOM-O
Pd(OAc)2, 25 °C
(104)
99%
O-TMS O
O [O] O
–H2
O [O] O
–H2
Scheme 5
N N N N
chloranil, C6H6, 20 °C
H H H H H H (105)
47%
O O
O O
H ddq, p-TsA, 25 °C H
(106)
90%
H H H H
O O
OAc OAc
EtO OEt
EtO silica, 20 °C O
(109)
OH 94%
O OH MeSO2Cl, Et3N O
(110)
85%
O O
Ph Ph
p-TsA, toluene, 110 °C
Ph Ph (111)
60%
OH
O O
O
mcpba O
n-C6H13 SPh (113)
75% n-C6H13
SPh
O– NC – O OEt i, HCl
+
ii, NaOH O
S + (114)
Ph 50%
O
Ph O
∆ Ph
(115)
80%
S
O O
117 a\b!Unsaturated Ketones
O SPh
SPh
CN
i, ButLi, THF i, HCl
SPh – CN N(Me)Ph
CN ii, mcpba
ii, N(Me)Ph
N(Me)Ph
O
Scheme 6
O i, NaH, THF
ii, H2O2, HCO3– O
+ But (116)
PhSe O 87% But
PO(OMe)2
i, MeI
ii, dbu
(117)
O
73% O
NMe2
dbu = 1,5-diazabicyclo[5.4.0]undec-5-ene
i, 3% Pd(PPh3)4
O ii, NH4Cl O
MgCl
+ (118)
n-C5H11 Cl 89% n-C5H11
O
O i, Et2O OH
ii, HO
+ (119)
B
n-C7H15 95%
OMe
n-C7H15
a\b!Alkenic Bond 118
i, BunLi
ii, ZnCl2
iii, alkenyl iodide, Pd(PPh3)4 O
O O iv, HCl
+ n-C6H13 n-C6H13 (120)
Br I
92%
O
O
IrH5(PPri3)2, 60 °C
(121)
92%
n-C8H17
n-C6H13
MeO2C
MeO2C OH
pdc, 25 °C
(122)
62%
O
pdc = pyridinium dichromate
2[94[0[1[4 From reactions of further unsaturated a\b!unsaturated acids and their equivalents with
carbon nucleophiles
These reactions are very similar to those used for simple a\b!unsaturated ketones "see Section
2[94[0[0[4#[ For example\ the lithio methylphosphonate in Equation "012# reacts with the dienoate
at the ester group to give the corresponding ketone ð73JA2764Ł[ The acid chloride can also be
used as the electrophile "Equation "013## ð35HCA693\ 41JCS2834Ł[ Nitriles "with Grignard reagents#
ð36HCA894Ł and amides "with organolithiums# ð79JCS"P0#1740Ł have also been reported[
O –78 °C O O
CO2Me + (123)
Li P(OMe)2 52%
P(OMe)2
i, Na, C6H6
O O ii, acid chloride
O iii, HOAc O
+ THP-O O-THP (124)
Cl 90% n-C6H13
n-C6H13
129 a\b!Unsaturated Ketones
2[94[0[1[5 By FriedelÐCrafts acylations of dienes
Acid chlorides and their equivalents have been reported to react with dienes to give further
unsaturated a\b!unsaturated ketones[ For example\ Naso et al[ have used the disilyl diene in
Equation "014#\ and were able to mono! and diacylate e}ectively ð80CC126Ł[ In other cases\ activation
of the double bond has been achieved by substitution with sulfur or nitrogen "Equation "015##
ð75TL242Ł[
i, AlCl3, 0 °C
O O ii, MeCOCl, AlCl3, 20 °C
TMS
TMS +
Cl OMe 39%
CO2Me (125)
S O O pyridine, CHCl3, 25 °C O S
+ (126)
S F3C O CF3 100% F3C S
O
OEt
EtMgBr, CuBr, –60 °C
Et
OEt
• (127)
77%
THP-O OH
THP-O
O
MeCOCl, AlCl3, –60 °C
(128)
TMS 60% •
i, NH3(l)
O O
ii, NH4Cl (aq.)
EtO
iii, HCl, H2O •
Ph + (129)
Na 50%
Ph
OMe
OMe
O 0.5% NaOH, 20 °C
+ O (130)
CHO O
O 71%
ButOK, ButOH, 20 °C
H (132)
H H
O 90% H
O
H OH
OH
p-TsOH
O (133)
84%
O O
O O O
(EtO)2P
O ButOK, ButOH, 20 °C O
+
PPh3Br– + Ph CHO (135)
19% Ph
(21)
121 a\b!Unsaturated Ketones
2[94[0[1[09 From pyrilium salts
The reduction of 1\3\5!trisubstituted pyrilium salts with sodium borohydride leads to 1\3!dienones
in moderate yield "Equation "025## ð51T146\ 61BSF1409Ł[ These pyrilium salts can also be cleaved by
a range of other nucleophiles including Grignard reagents\ amines and cyanide\ to give 3!substituted
1\3!dienones ð47BSF0347\ 50JCS2455\ 51LA"543#020Ł[ A related reaction involves the preparation of an
intermediate pyran which undergoes an electrocyclic ring opening to a substituted 1\3!dienone
"Equation "026## ð89CL002Ł[
OEt
i, p-TsOH, 50 °C
ii, TFA, CHCl3, 40 °C
O
+ EtSH (137)
74% F3C SEt
F 3C O OEt
O O
300 °C, PhH
(139)
64%
(22) (23)
MeO2C
MeO2C
O [Rh(OAc)2]2, 20 °C O
O
+ (140)
+ 80%
CHO
N N–
N– O
N+
[Rh(OAc)2]2, CH2Cl2, 20 °C
O (141)
95%
O CHO
a\b!Alkenic Bond 122
2[94[0[1[01 By Claisen rearrangements
The Claisen reaction can also be used to synthesise doubly unsaturated ketones in high yield from
propargylic alcohols via an intermediate isolable allene which is isomerised under basic conditions
"Equation "031## ð56HCA0047Ł[ Pyrolysis of propargyl acetoacetates results in a similar Claisen
rearrangement followed by decarboxylation to give doubly unsaturated ketones ð46JOC0500Ł[ The
sulfoxide "13# undergoes a zinc carbonate induced Claisen rearrangement and subsequent elim!
ination of benzene sul_nic acid to yield the ketone "14# in 74) yield "Equation "032## ð67CC597Ł[ An
exceptionally facile Claisen rearrangement has also been reported which yields a cyclohexadienone
ð65JOC567Ł[
SOPh
ZnCO3
(143)
O O
85%
(24) (25)
O
O
O O
320–330 °C
(146)
91%
Cl O
O
Cl BF3, 25 °C Cl
+ (147)
86%
PhSe PhSe
(26)
O O O
O
MeOH, 20 °C
+ (148)
90%
NH2 NH2
O MeO2C
THF, 20 °C
MeO2C CO2Me + NH2 (149)
63%
CO2Me
NH2 O
O
O
X base
R X
R
LG
(28)
X = halogen
Scheme 7
a\b!Alkenic Bond 124
Br O O
NaOAc, EtOH
Ph Ph Ph Ph (150)
94%
Br Br
(29) (30)
O O
pyridine, RT
Br Br (151)
80%
H Br H
O O
Br
collidine, 210 °C Br
Br (152)
90%
H H
O O
Cl
H2O2, pyridine, CH2Cl2 Cl
SePh (153)
82%
O O
py•HBr•Br2, pyridine Br
(154)
57%
H Cl
O
O LiCl, THF, 65 °C O
H (155)
80%
O OMe O OMe
O O-TMS O-TMS O
TMS-Cl, TEA CHBr3, KOBut PhH, reflux
Br
DMF 85–95% 86%
Br Br
Scheme 8
125 a\b!Unsaturated Ketones
Cl Cl
EtO Cl
NaOMe, DMSO
O (156)
2-9%
S
S
(31)
Br O Br
Br
EtO
AgNO3, EtOH
(157)
48%
N N
Ts Ts
(32) (33)
O O
(35) (34)
Cl O O
O Cl
Cl3CCOCl Cl CH2N2 Cr(ClO4)2 Cl
Cl 0 °C
Zn-Cu
RO Ar
O RO Ar Ar
(36)
Ph
Scheme 9
O O O
O i, BunLi, –90 °C PhCHO, 40 °C
P(OEt)3
Cl3C P(OEt)3 But Ph But
ii, ButCOCl, –125 °C 76% overall
Cl Li Cl
(37)
Scheme 10
a\b!Alkenic Bond 126
O O
O i, Cl2 PhCHO, 90–95 °C
PPh3
PPh3Br Ph
ii, NaOH 98%
Cl Cl
(38) (39)
Scheme 11
O O–
F CO2Et
O– F S+
CH2Cl2, Et2O Me
+ S+ Me (159)
Me 93%
Me
F X
OLi F OH F X
O F Li R1 i, R3Li R1 96% H2SO4
R1 O
R2 F R2 R3
R1 R2 X = F, Cl ii, H3O+ –30 °C
X X R2 R3
(40)
Scheme 12
F F F F
F OH MeLi, RT H2SO4, 100 °C, TCE
OH O
56%
F F
(41)
Scheme 13
Scheme 14
127 a\b!Unsaturated Ketones
+
S
Me2N
Cl O
O O
(44) (45)
R1 O O
O
35 °C Cl R1
+ • R1 + Cl (161)
Cl Cl
Cl Cl
R2 R2 R2
O O
AlCl3, acetylene
(162)
Cl 60%
Cl
Cl O Cl O
AlCl3, (CHCl2)2
(163)
64%
S S
Cl
O AlCl3
+ Cl (164)
Cl Cl Cl 80%
O
A highly ~exible general route to b!halo!substituted a\b!unsaturated ketones that can give good
yields of either "E# or "Z# isomers is the addition of HX to an alkyne ketone "Scheme 04#
ð58JCS"C#0193Ł[ Kishi et al[ have shown that TFA solutions of sodium iodide give good yields of the
"E#!iodo vinyl ketones "35# "Scheme 05#\ but in acetic acid the major product is the "Z# compound
"36# ð75TL652Ł[ The reaction will work even on disubstituted alkynes with TMS!I etc[ to give the
"E#!b!iodo vinyl ketones "37# "Equation "054## ð75TL3648Ł[ Alternatively\ the intermediate iodo!
metallated species can be trapped by other electrophiles "Scheme 06# ð75TL3656Ł[ The hydro!
chlorination of allenic ketones has been investigated and is useful for the preparation of the b!"E#
isomers "Equation "055## ð72BSF"1#78Ł[
a\b!Alkenic Bond 128
O
HX (or DX)
20 °C R X
O
R
O X
HX (or DX)
–40 °C
R
Scheme 15
O
NaI, TFA
95% n-C5H11 I
O
(46)
n-C5H11
O I
NaI, AcOH
70%
n-C5H11
(47)
Scheme 16
O O
TMS-I I
O O (165)
O O
(48)
O OH
O OM
MI, M = TMS, Et2Al or Bun4N RCHO
n-C5H11 R
n-C5H11 n-C5H11 • I
I
Scheme 17
Cl
• SnCl4
(166)
82%
O
O
H O H O H Cl
LiH
+ (168)
PhOPOCl2
H O H Cl H O
EtO2C EtO2C EtO2C
2:3
O O
PCl3, CHCl3
(169)
O Cl
O O Cl
CHO (COCl)2
(170)
O O
Ph3PBr2
(171)
O Br
(E):(Z) 93:7
O O
BF3•Et2O, PhCH2NEt3X
(172)
72–93%
Ms X
X = Cl, Br, I
O
O
Cl PdCl(PPh3)2CH2Ph, C6H6
+ O (174)
95% O O
O SnBu3 O
O
(49)
a\b!Alkenic Bond 130
ButLi, THF
+ (175)
59%
O OH
O O O
O
O
O
AlCl3
+ n-C5H11COCl n-C5H11 (176)
66% O
O TMS
O
O O O
O Zr(OPrn)4
i, O
ii, NaOMe
(178)
63% H
MeO MeO
O O
trans : cis 25 : 1
O
O
O MeO
OMe KOEt
+ (179)
57%
MeO
N O OMe
AcOH
+ OMe (180)
69%
O
O
O
i, EtOH
ii, HCl
+ O (181)
O 83%
OMe
OMe
131 a\b!Unsaturated Ketones
O O
OH Ph
MeOH O
Br + PhCHO (182)
89%
O O
O O
i, Hg(OAc)2
ii, CaO
Ph (183)
54%
MeO O Ph
MeO OH
O O
SPh i, Pb(OAc)4 OAc
ii, mcpba
(185)
86%
OCOPh OCOPh
S N Me i, HCHO, HCl O
ii, dbu OMe
(186)
N
N 78%
OMe
Br
(50)
a\b!Alkenic Bond 132
"vi# Miscellaneous methods
Additions of Grignard reagents to a!alkoxyacrylonitrile give good yields of the a!alkoxy!
vinylketones "Equation "076## ð60CR"161#0934\ 72JCS"P0#50Ł[ Transition metal catalysed carbonyl inser!
tion reactions have been investigated\ including the Pd!catalysed coupling reactions of a!
alkoxyvinylstannanes and vinyl tri~ates "Equation "077## ð89JOC2003Ł\ and intramolecular PausonÐ
Khand reactions ð89TL6494Ł[ A Wittig!type reaction has also been described ð64TL3242Ł[
i, MgBr O
NC OEt
OEt (187)
ii, H+
O
O2SCF3 EtO SnMe3 CO, Pd(PPh3)4, LiCl, THF OEt
+ (188)
82%
OMe O
PhH, ZnCl2, 20 °C O
+ (189)
87%
OBn
O
TMS-O OBn
(51)
OMe H O
H O O
O PhH, ZnCl2, 20 °C
+ (190)
O 72% O H
TMS-O O
OMe
O
ZnCl2, THF, 25 °C
+ Ph Ph (191)
O O
83%
TMS-O
(52) (53)
133 a\b!Unsaturated Ketones
The introduction of further oxygen functionality into the diene has also proved successful[ Thus
the diene "43# gave the oxygen!substituted pyrone "44# "Equation "081## ð73JOC281Ł "reaction of this
diene with an ordinary dienophile also leads to an oxygen!substituted enone system ð67JOC268Ł#\
whereas the diene "45# gave the cis!pyrone "46# which has been used in the total synthesis of
lincosamine "Equation "082## ð74JA0163Ł[ The diene "45# has also been substituted with further
unsaturation in the form of an aromatic system ð77JA2818Ł[ Asymmetric induction has been observed
via the use of chiral Lewis acid catalysts ð77JA209\ 78TL0078Ł\ and some ketones have been reported
to act as dienophiles for this cyclocondensation ð76CC645Ł[
OMe MeO O Ph
O Eu(fod)3, CDCl3
OMe + (192)
Ph 85%
TMS-O O
(54) (55)
fod = 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedionate
OMe
i, BF3•Et2O
O
ii, TFA
+ O (193)
67%
TMS-O BzO
OBz O
(56) (57)
MeO i, BunLi
ii, K2CO3, MeOH O
+ (194)
iii, HClO4 O
O O O
(58)
(59) (60)
O O O
K2CO3, DMF, 115 °C
(EtO)2P O But (196)
70% But
O O
Scheme 18
O i, Br2, CCl4 O
ii, NaOH, EtOH
Ph (197)
90% Ph
OH O
OMe O
• p-TsOH, H2O, MeCN, 100 °C
Ph (198)
MeS Ph 93%
Ph OH O Ph
(62)
Br Br O
Me2NCHO, Fe2(CO)9
(199)
64%
O O
O i, NaH, DMSO, 95 °C O
ii, H2SO4
O (200)
62%
O O
(63)
O Cl O OBut
OMe OMe
(64)
OEt O
O pyridine
+ (202)
79%
Cl3C OEt
Cl3C Cl
(65)
O
OMe pyridine, CHCl3
+ (CF3CO)2O CF3 (203)
OMe 94%
MeO
O O
Et2O
+ Cl (204)
Cl
Ph O-TMS 85%
Ph O
O O
O
O O O
MeLi CO2Et
CO2Et + (206)
Ph Cl Cl 52%
O O Ph
O
O O Mg(OEt)2 CO2Et
+ (207)
CO2Et 50%
Cl
O
a\b!Alkenic Bond 136
"vii# From ð1¦1Ł cycloaddition reactions between alkoxyalkynes and ketenes
Alkoxy and siloxy alkynes add smoothly to ketenes leading to 2!alkoxy!1!cyclobutenones "Equa!
tion "197## ð47RTC650\ 62JOC0340\ 74S0007\ 77JA2582Ł[
O
CH2Cl2
ButO + H2C • O (208)
70%
ButO
O O O
MeO
+ O O (209)
80%
O O-TMS MeO
O OH O
(67)
O O
KOH, MeOH
+ (210)
S CHO S S
S
(69) (68) (70)
137 a\b!Unsaturated Ketones
O R
O
NaOH (aq.), EtOH
+ R O (211)
S
S
R
(71) (72)
R = Ph,
O
NO2
CHO O O
O OH
Ac2O, AcOH, 120 °C
+ (212)
82% S S
S S
NO2
(73)
O2N
(74)
O Cl Cl
Cl Cl
Cl
Cl CHO
S
O BF3•Et2O
86%
S O
O
O S
HCl, AcOH, 110 °C
87%
S O
Scheme 19
O O OHC CHO
S morpholine
+
84%
N
Cl Cl H
(75)
O O
S
(213)
Cl Cl
N
H
(76)
O
CO2Et
NaH, DMSO, THF
SO2Me (214)
70%
CO2Et
SO2Me
a\b!Alkenic Bond 138
O
S i, ButLi
ii, AcCl, 70 °C S
O (215)
33% OH
S
S
(78) (77)
O SMe
S
Me p-TsOH, PhH, 80 °C H
O (216)
O 75%
O O O
O
S O S O
I2, MeOH
(218)
Ph3CO Ph3CO
(80) (79)
O O
PhSCl, MeCN, 20 °C
SPh (219)
60%
(81)
O O
NaOH, EtOH, 20 °C S
+ SH (220)
O 81%
Cl
Cl SCl Cl S
Ar
Ar Ar
O
O O
H
Cl S Ar S
Ar
H O O
Scheme 20
NO2
S
SOCl2, pyridine, 70 °C
O (221)
43% O2N
OH O
dabco, RCHO Jones oxidation
PhSO2 PhSO2 PhSO2
R R
(82) (83)
dabco = 1,4-diazabicyclo[2.2.2]octane
Scheme 21
Li But O
ButCOCl (85), THF, –80 °C
CO2Me CO2Me (222)
PhS 72% PhS
(84) (86)
Thermal rearrangement of the diazoketone "76# gives a quantitative yield of the ketone "77#\ and
the reaction is postulated to proceed via a Wol} rearrangement involving a selective shift of the
sulfur bridge "Equation "112## ð79JOC3793Ł[ A similar rearrangement occurs with the ketone "78# in
the presence of triphenylphosphine dibromide^ this reaction is thought to involve an unstable
sulfonium salt formed by transannular reaction "Equation "113## ð58RTC883Ł[ 1!Sulfonyl!a\b!unsatu!
rated ketones can be prepared by the oxidative ring cleavage of 3!isoxazolines with mcpba in
excellent yield[ The starting isoxazolines are easily prepared by the cycloaddition of nitrones and
alkynes "Equation "114## ð76TL802\ 77JOC1127Ł[ Additions of 0!lithio!0!phenylpropa!0\1!diene to
ketones\ followed by tri~uoroacetylation\ 2\2!rearrangement and methanolysis of the resulting
dienol tri~uoroacetate\ lead to the C!2 homologated a!phenylthioenones in moderate yield "Equation
"115## ð72CC374Ł[ An exactly analogous reaction has been achieved by the photolysis of a diketone
with a sulfur substituted alkyne^ this reaction is thought to proceed via ring cleavage of an inter!
mediate oxete "Equation "116## ð63TL3068Ł[ An excellent yield of the 1!alkylidene!3\4!dihydro!
thiophen!2!one "89# can be obtained by the cyclo!condensation of a!thiolcinnamic acid "80# with
the nitrostyrene "81# under DeanÐStark conditions "Equation "117## ð62IJC017Ł[
a\b!Alkenic Bond 140
N–
O
O N +
99 °C
(223)
100%
S
S
(87) (88)
O OH
O
Ph3P•Br2, DMF, 153 °C
(224)
55%
S
S
(89)
Me
Ph Ph
N
mcpba, 25 °C PhSO2
O (225)
PhSO2 98%
O
i, TFAA, 0 °C O
O PhS Li ii, 65 °C SPh
iii, MeOH, K2CO3
+ •
(226)
47%
O SBut O
O
hν, PhH
Ph + (227)
Ph Ph SBut
45%
O Ph
S Ph
SH PhH, 80 °C
Ph + Ph Ph
O2N (228)
CO2H 90%
O NO2
(91) (92) (90)
O i, NaH O
ii, CS2
CN iii, MeI CN
(230)
75%
Ph Ph S SMe
(93)
O S
S DCM, 20 °C
BF4 –
+ +
S
(231)
S 74%
O
(94) (95)
OH O O
FeCl3, 20 °C
(232)
HO2C S S S
HO2C CO2H
(96) (97)
Cl S
SH
NaOEt, EtOH, 20 °C
+ (233)
100% NH2
NH2
O O
(99) (98) (100)
Cl NaOH (aq.), 25 °C O
ButSH + (234)
O 85% SBut
(101) (102) (103)
O EtOH, reflux O
+ + HS CO2Et (235)
NEt3 82% S CO2Et
(105) (106) (104)
SH O O
NaOMe, MeOH, 20 °C
+ (237)
50%
S S
NH2
NH2 NH2
(99) (109) (110)
O
Na2S2, MeOH, 20 °C
O
S S
(238)
94%
CF3
O
(111) (112)
143 a\b!Unsaturated Ketones
R CO2Et O
NaH, DMSO, 0 °C R
(241)
EtO2C 82%
SEt EtS CO2Et
NO2 H O
O
AgBF4, CH2Cl2, –25 °C
Cl + (242)
TMS S 58%
NO2 H SAr
MeO2C CO2Me
MeO2C CO2Me O O
S S
Et3N, 5 °C
S S + (243)
100%
+ O
PBu3
OMe
O O
O NaNH2, PhH, 20 °C Ph OMe
+ (244)
S 80%
+ Ph S S S
PPh3
(116) (117) (118)
S
MeS NaH S S
O
S + O (245)
Ph3P + 79%
R O
R SMe
(119) (120) (121)
Ph
SMe
O NaOEt, EtOH
+ HO2C O (246)
Ph S+ Ph 46%
S Ph S
S
(122) (123) (124)
Ph Ph O
i, 2N KOH
(247)
S+ ii, PhCH2Cl, 20 °C Ph S Ph
Ph S
S S S H2SO4, H2O
S S O
(248)
Ph Ph
Ph
+ O (249)
S N2 S
S S O
S Ph
dbn = 1,5-diazabicyclo[4.3.0]non-5-ene
+
N Et3N, CH2Cl2 O O
+ (251)
S O 56%
O O S O
Ph
Ph
Thiapyrylium iodide reacts in a similar fashion to 0\1!dithiolylium salts with activated methylene
compounds "Equation "141## ð63BSF0085Ł[ Treatment of pyran!3!thiones with sodium hydrogen
sul_de and subsequent oxidation yields dithiolidene ketones in good yield "Equation "142##
ð53BSF2143\ 69JCS"C#1301Ł[
Ph
Ph O
pyridine O
+ Ph (252)
97%
+
CN Ph S Ph
Ph S S–
CN
145 a\b!Unsaturated Ketones
S Ph
i, NaSH
ii, K3Fe(CN)6
O (253)
67% S
Ph O S
TBDMS-O SPh
PhS Li
–50 °C
+ MeO2C O-TBDMS (254)
70% MeO2C
CO2Me
O
(128)
O
O
CO2Me
TMS-Cl, DCM, 42 °C CO2Me
(255)
74%
S
S
O
(129) (130)
TEA, CH2Cl2
O SO2Ar (256)
95% O SO2Ar
I
(131) (132)
TEA = triethylamine
i, NaNH2 S S
O ii, (NH4)2S2O8
+ CS2 S (257)
But But
But 34%
O O
O
OH O O
i, mcpba
ii, pyridine OH
O O (259)
78%
O
SePh SePh O
O O O
piperidine
+ O (260)
71% NH
Se N Se
H
O
O O
O Nsubst.
R3 R2
Nsubst. R1 (262)
R1
R3 R2
O
O O
Et3N, DMF
+ N (263)
N 88% H
O NMe2
NMe2
(133) (134)
O O
C6H6
+ (264)
N S CHO 74% N
H
S
O
(135)
147 a\b!Unsaturated Ketones
O O
Ph
+ PhCHO (265)
60%
N N
Ts Ts
(136) (137)
Bender et al[ showed that the "Z# geometry was exclusively obtained on condensation of the
quinoline aldehyde "027# with the quinuclidone "028# "Equation "155## ð57JOC1493Ł[ A mixture of
"E#:"Z# isomers can be prepared by treating "039# with acid\ but the "E# isomer is unstable and
slowly rearranges to the "Z# compound[ a!Pyridinium salts "e[g[ "030## also react well with aldehydes\
giving the highly coloured betainecyanine "031# in excellent yield "Equation "156## ð59CB0957Ł[
O
CHO
O
MeO NaOEt N
+ (266)
91% MeO
N
N
N
(138) (139) (140)
O Me
O +
N Ph
N
O
Ac2O Br
+ (267)
96%
Me N +
N
Br
Ph
(141) (142)
a!Nitro substituted a\b!unsaturated ketones have been reported[ For example\ nitroacetone "032#
reacts with the imine "033# to give a mixture of "E# and "Z# isomers of the nitro!substituted ketone
"034# "Equation "157## ð46LA"591#03Ł[ Apparently\ if the aldehyde derivative of "033# is used\ reaction
occurs at the methyl group of the nitroacetone[ Nitromethyl 0\3!diketones\ for example "035# have
been cyclised to give the novel nitro!1!cycloalkene!0!ones "036# in good yield "Equation "158##
ð80S518Ł[
Bu O
N
NO2
O Ac2O
+ NO2
(268)
69%
Cl Cl
(144) (143) (145)
O
K2CO3, MeOH
O (269)
87%
O NO2 NO2
(146) (147)
Azidoacetophenones "037# have been reported to react with substituted benzaldehydes to give
a!azidovinylketones "038# "Equation "169## ð69M046Ł[
a\b!Alkenic Bond 148
O
CHO
N3
O Ph
N3 + (270)
Ph
X
X
(148) (149)
(150) (151)
I N3 N3
Ph IN3 Ph + Ph Ph
83%
O
O N3 O I O
(152) (153) 40 : 60 (154) (155)
Scheme 22
O O
NaN3, HN3, DMF
Ph Ph (272)
72%
Br N3
(156)
Cl O
Me i, Mg, THF Me
N ii, Ac2O (158) N
(273)
56%
(157) (159)
159 a\b!Unsaturated Ketones
O O Ph
i, ButLi, –110 °C O
ii, PhCO2Me
Et2N N (274)
87% Et2N N
(160) (161)
OMe
O H
N C6H6
O O
+ OMe OMe (275)
85% N
MeO
i, NaNO2
ii, H2, PtO2
O O (276)
90%
NH2
O OH
(165)
O HN
N2+ Ph N
H
O HN N
DMF, EtOH N
+ (277)
Ph N 67%
H
Br
Br
(166) (167) (168)
Ag2CO3
(278)
N 57% N
H H
OH O
(169) (170)
a\b!Alkenic Bond 150
2[94[0[6[1 2!Nitrogen!substituted a\b!unsaturated ketones
The chemistry and reactions of enaminones have been reviewed ð35CRV72\ 66CSR166Ł[
R22N
R1COCl
R22N R1 (279)
O SnCl4, CH2Cl2
+ (280)
N 58%
Cl N
CO2Me
CO2Me
(171) (172)
COCl
O
Et3N, CHCl3
NEt2 + (281)
Ph Ph NO2
32%
NEt2
(173) NO2
COCl
O
MeHN Et3N, toluene MeHN
+ (282)
62%
CO2Me CO2Me
(174)
F
NO2 COCl
O
NMe2 F Et3N, C6H6 NO2
+ (283)
NMe2
(175)
(176)
151 a\b!Unsaturated Ketones
Intramolecular cyclisations of an enamine and acylating agent are well known\ generally with an
ester as the acylating group[ In Equation "174# the N!b!carbomethoxyethyl enaminone "066# is
cyclised to the dihydro!3!pyridone "067# in good yield ð50JPR183Ł[ Similarly\ the N!b!carbo!
ethoxyethyl pyrrolidone "068# a}ords the hexahydro indolizine "079#\ via a mixed anhydride
"Equation "175## ð79TL0262Ł[ In addition\ the enamine can be prepared in situ and cyclised directly[
For example\ substituted cyclohexanones react with pyrrolidones and cyclise under the action of
catalytic p!TsOH "Equation "176## ð65JCS"P0#893Ł[ The b!aminoester "070# in Equation "177# con!
denses and cyclises\ in the same manner\ with cyclopentanone "or cyclohexanone# ð68JHC416Ł[
O
MeO2C CO2Me
MeO2C
NaOMe, MeOH
(285)
N 84%
H N
Ph H
Ph
(177) (178)
EtO2C
i, NaOH
N ii, Ac2O, MeCN EtO2C
N (286)
71%
O
CO2Et
(179) (180)
O
O
p-TsOH N
+ CO2Me (287)
N 60%
H
N
N
TFA, toluene N
NH + (288)
81%
O
CO2Me
O
(181)
Alternative tactics for performing the acylation of an enamine or derivative have been investigated[
Formation of an organometallic reagent such as a lithium derivative directly from the imine followed
by the addition of an ester gives excellent yields of the enaminone "Equation "178## ð89S784Ł[ The
"Z#!enaminone can be formed stereospeci_cally and in good yield under more mild conditions if the
intermediate vinyl bromide is formed _rst\ as in Equation "189# ð72JCR"S#111Ł[ This reaction would
appear to be very useful\ since other methods of preparing N\N!dialkylenaminones would give the
"E# isomer[ A related reaction that has been observed to proceed quite well is the oxidation of
tertiary amines to give "E#!enaminones "071# "Equation "180## ð70TL712Ł[
Ph
i, LDA
ii, PhCO2Me
O (289)
N NH
86%
i, Br2
ii, Et3N
O iii, BunLi Et2N
Et2N + (290)
But Cl 80% O But
a\b!Alkenic Bond 152
O
Cl3C CCl3
N N CCl3 (291)
65%
O
(182)
O O R32NH O NR32
(292)
R1 R2 R1 R2
O O O NHEt
EtNH2
(293)
96%
(183) (184)
O O O NEt2
Et2NH
(294)
65%
O NH2
NH4OAc
Ph Ph (295)
97%
O O
MeNH2, AcOH
O O O NHMe (296)
90%
(185)
NHPh Ph
O N Ph
Ph
AcOH, NaOAc
O (297)
O 35%
Ph Ph
O O
For open chain 0\2!dicarbonyl compounds the simplest cases of amination are for symmetrical
0\2!diones[ Thus aqueous ammonia and acetoacetone a}ord the enaminone "075# very conveniently
"Equation "187## ð89S784Ł[ In non!symmetrical cases\ the most electrophilic carbonyl group seems
to be aminated[ For example\ in "076# "Equation "188## ð73S552Ł\ the carbonyl group next to the methyl
group is aminated\ and similarly in Equation "299# ð56JOC2706Ł[ The stereochemistry can depend on
the solvent\ with internal hydrogen bonding providing cis isomers in many cases ð63JPR358Ł[
153 a\b!Unsaturated Ketones
O O NH3 (aq.) O NH2
(298)
90%
(186)
O O NH2 O Ph
xylene
+ (299)
Ph Ph CO2Et 81% Ph N CO2Et
H
(187)
Other nitrogen nucleophiles that have been used include hydrazones and hydroxylamines[ Thus
cyclohexane!0\2!dione reacts with N!methylhydrazones "077#\ but only in moderate yields "Equation
"290## ð62CB349Ł[ Similarly\ phenylhydroxylamine "078# gives the N!hydroxyenaminone "089# in
excellent yield "Equation "291## ð62TL3422Ł[ The purpose of the ascorbic acid in this reaction is to
prevent decomposition of the phenylhydroxylamine[
Me
O O TsOH, C6H6
NHMe O N
+ Ph N N Ph (301)
30%
(188)
OH
O O ascorbic acid, C6H6 O N
+ PhNHOH Ph (302)
93%
(189) (190)
A reaction related to the amination of 0\2!diones is the intramolecular cyclisation of nitriles with
0\2!diones\ for example "080# in Equation "292# gives the dihydropyridone "081# ð54TL1150\ 65JOC525Ł[
CN
O
MeCOCl
O N (303)
O O H
39%
(191) (192)
In addition to using the 0\2!diones directly\ b!alkoxy!a\b!unsaturated ketones have been used[
Stereoselectivity is observed in some cases\ but not in others[ In this respect\ cyclic alkoxyenones
are the simplest and can give excellent yields of enaminones with amines[ For example\ the
alkoxycyclopentenone "082# gives the aminocyclopentenone "083# when reacted with ammonia
under pressure "Equation "293## ð80S065Ł[ Alternatively\ the alkoxyenone can be formed in situ and
reacted directly with a nitrogen nucleophile "Equation "294## ð70S114Ł[ The same method may be
used for open chain compounds\ for example "084#\ and gives the "E# compound under these
conditions\ as expected for dialkylated enaminones "Equation "295## ð77S027Ł[ DMF acetals have
also been used ð68T0564\ 79JOC3411\ 71SC24Ł[
O O
NH3
(304)
95%
OEt NH2
(193) (194)
a\b!Alkenic Bond 154
O NH2
O O O AcOH, DMF
N
H
+ (EtO)3CH + (305)
H2N NH2 85% O O
O O
(EtO)3CH, Et2NH
Et2N (306)
44%
(195)
Reaction of the alkoxyenone "085# with a primary amine "086# leads to the formation of the "Z#
enaminone "087# in quantitative yield "Equation "296## ð78TL5062Ł[ The "Z#!enaminone is also
reported by Tietze et al[\ from the reaction of benzylamine with the alkoxyenone "088# "Equation
"297## ð78CB72Ł[ Dialkoxyenones "ketene acetals# also undergo the reaction and are reported to give
the "E# isomer "as shown# in most cases "Equation "298## ð89S084Ł\ even though this is an N\N!
dialkylenaminone[
CF3
EtO CF3
+ NH2 N O (307)
O H
O
O
PhCH2NH2 MeO2C
MeO2C H (308)
87% N
EtO
Ph
(199)
Gerus et al[ have reported that the reaction of the "E#!enol ether "199# gives rise to the
"Z#!enaminone "190# when a primary amine is used\ due to internal hydrogen bonding\ but secondary
amines "such as pyrrolidine# give the "Z# product "Equation "209## ð80S196Ł[ Silyl enol ethers can
also be used "Equation "200## ð78CB72Ł[ In addition to alkoxy derivatives of 0\2!dicarbonyls\ other
heteroatom based leaving groups have been investigated "e[g[ S or N#[ Equation "201# illustrates the
transformation of a ketene S\S acetal "191# into a ketene S\N acetal "192# ð66JPR434\ 89S051Ł[ Sulfonic
acid and sulfones have also been used as the leaving group "Equation "202## ð67TL632\ 89JCS"P0#0780Ł[
CO2H
CO2H
O 1N NaOH H
+ O N (310)
NH2
F3 C OEt 89%
F3C
(200) (201)
NH2
H OMe
O O-TMS CH2Cl2 O N
+ (311)
88%
OMe OMe
OMe
155 a\b!Unsaturated Ketones
MeS O EtOH S O
+ NH2 (312)
HS
MeS O 92% N O
H
(202) (203)
O O
O O
PhNHMe, Ni(OAc)2, AcOH
(313)
42%
SO3– N(Me)Ph
O
O
EtOH
+ But NH2 (314)
79% But
N
Br
H
O
NH2 H
O Et3N N
+ (315)
N Cl 92%
H N
H
O Me3N
O
+ (316)
Cl 88% NMe3
OMe NMe2
OMe OMe
Me2N
OMe
(318)
O O
(204)
a\b!Alkenic Bond 156
Me2N
Me2N
O OBut
Me2N
O (319)
95%
Thio!substituted ketones also work well "Equation "219## ð76S785Ł[ Variations on this reaction
include the use of other aminomethylenating agents for which conditions have been reported that
can select one carbon of an unsymmetrical ketone\ and the use of the novel N!acyl imido!
thiocarbamate "194# under basic conditions to give the cis compound "195# "Equation "210##
ð72JOC512Ł[
OMe O
O Me2N
OMe PhS OEt
PhS OEt (320)
100%
O
O Me2N
Ph O Ph
N SEt ButOK, THF H
O N (321)
78% O
O SEt
O SEt
(205) (206)
OMe O OMe O
Et2NH, MeOH
NEt2 (322)
O H Ph
O N
PhNH2
(323)
75%
MeO MeO
O O
Me3NH+ BF4– (207), MeOH
+ (324)
58% NMe3
O
O Et3N
+ MeNHNO2 NO2 (325)
Ph N
Ph
Me
157 a\b!Unsaturated Ketones
"v# Reactions of ketones with a cyano compound
Nucleophilic addition of an enolate to a nitrile leads to an enaminone\ "Equation "215##
ð66H"5#0874Ł[ Interestingly\ b!diketones such as "197# can add to benzoyl cyanide at the cyano
carbon\ when Ni"acac#1 is used as a catalyst "Equation "216## ð73CC0482\ 73JOC3585Ł[ Tin"IV# chloride
also catalyses the reaction\ and in these cases the nitrile seems to need further activation by an
electron withdrawing group\ for example CO1Et\ etc[ "Equation "217## ð77JCR"S#135Ł[
O MeNH2
+ O (326)
O CN 80%
NH2 O
O O
O O O Ni(acac)2 Ph
+ (327)
Ph CN Ph 87% Ph
H2N
(208) O
O CCl3
O O SnCl4
Cl3C CN + NH2 (328)
O
Ph3P
Ph
(209)
O N (329)
O N O 17% H
H Ph
O
(210) (211)
O
O PPh3
N (330)
56% N
O
O
O
O OMe
OMe O i, RT
N S
Br ii, PPh3, Et3N N
+ (331)
88%
CN CN
a\b!Alkenic Bond 158
"vii# From ketenes and an enamine
Ketenes react with enamines at 9>C to give cyclobutanones which spontaneously ring open to
give the b!enaminones in excellent yield "Equation "221## ð50JOC3664\ 51AG21\ 52LA"551#067Ł[ This
reaction is similar to the acylation of an enamine which has already been discussed in "i# above[
NMe2
OMs
N
N O-TMS
+
Et2AlCl
O
H
N N
90%
O
Scheme 23
Ph
169 a\b!Unsaturated Ketones
i, Pri2NEt O O
BuO O O ii, HCl (aq.), THF P(OEt)2
+ (334)
P(OEt)2 78%
b!Phosphorus substituted enones can be made by the oxidation of an alcohol^ the reaction
incorporates an allylic transposition "Equation "224## ð80S246Ł[ Arbuzov reactions starting from
b!halovinyl ketones and Wittig!type alkenation are also known ð68LA381\ 74M66Ł[
O
O
(MeO)2P OH CrO3
(335)
76% P(OMe)2
O
TMS TMS O
TMS Co
Co2(CO)6, 22 °C Co CO(g), Bu3PO, 85 °C H
O H H
94% 51%
O O
O
O O
Scheme 24
(215) (216)
Scheme 25
O O O
O H
TMS • CHCl3, 25 °C
TMS
+ O O (337)
89%
O H O
(217)
i, BunLi, –95 °C
OMe ii, TMS-Cl
Br iii, MeOH, K2CO3 O
(338)
Br 57%
H TMS
(218) (219)
Scheme 26
Silyltin alkenes are readily available by the addition of silylstannanes to terminal alkynes under
palladium catalysis\ and they undergo e.cient Stille coupling reactions with acid chlorides to
give 2!silyldivinyl ketones "Equation "228## ð75TL1790Ł^ see also ð73JA6499\ 75JOC2450\ 89SC0554Ł[ A
conceptually similar approach involves the coupling of a b!silylvinyl cuprate\ derived from the
addition of a silyl anion to a terminal alkyne\ with an acid chloride ð79CC165\ 77HCA057Ł[ Vinyl
silanes can also be acylated with acid chlorides in the presence of Lewis acid catalysts ð71TL0834\
77TL774Ł[
161 a\b!Unsaturated Ketones
PhS OMe BunLi, R1X PhS OMe SiO2, hexane
R1
TMS TMS
(220)
Scheme 27
SnMe3
COCl PdCl2(MeCN)2, 60 °C
+ (339)
87% O
TBDMS
TBDMS
O
Rh(1), O2, 97 °C
(340)
83%
TMS
TMS
O
O
• TMS TiCl4, –50 °C
+ (341)
TMS 56%
TMS
(221) (222)
O Ph
O
Ph
RhCl(PPh3)4, 140 °C RhCl(PPh3)2
(342)
89%
S Ph Ph
S
O O
(223) (224)
Ph
N(Me)OMe THF, 20 °C
+ Ph Li (345)
Ph O 97%
Ph O
O
O (Ph3P)2PdCl2, CuI, Et3N, 20 °C
Ph + Ph (346)
Ph Cl 96%
Ph
The acylation of tin alkyne compounds requires palladium catalysis if the alkyne is carbon!
substituted ð71JOC1438\ 74HCA227Ł[ However this is not necessary if the alkyne is activated with a
heteroatom "Equation "236## ð79JOM"073#206\ 70LA0896\ 70TL1526\ 77CB1052Ł[ Other less widely used
acetylides for which acylations have been reported include] manganese ð74S49\ 78TL2434Ł\ zinc
ð77JOM"227#178Ł\ silver ð45JA0564Ł\ boron ð56AG"E#73Ł and vanadium\ which undergoes oxidative
addition to aldehydes in good yields "Equation "237## ð75TL822Ł[ The acylation of silyl acetylides is
carried out with Lewis acid catalysis and usually involves the use of aluminum trichloride with an
acid chloride "Equation "238## ð52CB2179\ 68S327\ 70S18\ 74S851\ 75HCA459Ł\ intramolecular examples
have been reported ð67TL1290Ł[ Silver tetra~uoroborate as Lewis acid with a thioester acylating
agent is also e}ective with silyl alkynes ð72TL4020Ł\ and the use of titanium tetrachloride with
diketene is also known ð76S0981Ł[
163 a\b!Unsaturated Ketones
Me
O Cl Me N
Et2O, 0 °C Ph
+ Bu3Sn N O (347)
57%
Ph Cl Ph
Ph Cl
i, VCl3, CH2Cl2
ii, PrnCHO, –78 °C to 40 °C
BrMg Bun (348)
63% O
Bun
O
TMS O
AlCl3, CH2Cl2, 0 °C
+ (349)
Cl 89%
TMS
TMS
O Br i, ButOK, DMF O Ph
ii, Et3N, 20 °C
Ph
(350)
100%
O Br O
i, Br2
ii, Et3N
O iii, ButOK O
Me2N (351)
Me2N 70%
O
OMe O
O OMe
+ Ph
K2CO3, MeOH, 60 °C
+ Ph3P (352)
Ph
66%
I
OMe
OMe
O
O OH KF, MeCN, Et2NCF2CFHCF3, 20 °C
(353)
Ph 72%
Ph
i, C6H6, 80 °C O
O O
+ ii, 200 °C
+ Ph3P CHO + (354)
n-C3F7 Cl – 85% n-C3F7
n-C3F7
1:1
a\b!Triple Bond 164
2[94[1[2 By Oxidation of Alkynic Alcohols and Propargylic Methylene Groups
Oxidations of alkynic alcohols proceed in much the same way as oxidations of allylic alcohols
"see Section 2[94[0[0[5#[ Manganese dioxide is a common reagent "Equation "244## ð53JA360\ 62CB28\
68CL0910\ 78HCA006Ł^ see also ð76JOC1426Ł for a ring opening reaction of cyclohexadienols using
MnO1 and ð49JGU0151Ł for use of a Mn"OAc#2 reagent[ Chromium trioxide:pyridine has been
used in several cases ð35JCS28\ 70JA3486\ 75S073Ł\ and other reagents used include ortho!chloranil
ð45JCS2969Ł\ oxalyl chloride:DMSO ð73JA4474Ł\ Na1WO3 ð75TL494Ł and electrochemical oxidation
ð89JOC2547Ł[
i, BuLi, THF O
EtO OEt ii, aldehyde
O iii, MnO2
+ Ph
OEt (355)
Ph 89%
OEt
The methylene group adjacent to a triple bond has been oxidised with chromium trioxide:pyridine
to a}ord an alkynone "Equation "245## ð60TL3268Ł^ t!butyl hydroperoxide can be used similarly
"also for terminal alkynes# ð77TL1210\ 78SC1950Ł[ In a related oxidative procedure\ Brown et al[ have
used the hydroboration of a haloalkyne to give a bromoalkenylborinate intermediate\ which was
then reacted with a lithioacetylide[ Oxidation of the resulting alkynenylborinate with H1O1:NaOH
gave the ynone "Equation "246## ð72S774Ł[
CrO3•pyr•2, 25 °C
(356)
42%
O
O
i–iv
+ (357)
Br Li
i, PriCMe2BHCl•SMe2, BBr3; ii, PriOH; iii, RLi, THF; iv, NaOH, H2O2
2[94[1[3 By Reaction of a Carbon Nucleophile with Alkynic Acid Halides and Derivatives
The reactions of alkynic acid halides "e[g[ Equation "247## with carbon nucleophiles have been
reported ð41JCS2834Ł[ Other similar examples using an alkynic ester and an enolate as the nucleophile
are known ð63JHC0090Ł[ Dimethyl alkynedicarboxylate reacts with certain enamines at the ester
group to give alkynic ketones ð71CPB52Ł[ The propargylic dithiane in Equation "248# can be
deprotonated and alkylated in an umpoled carbonyl synthesis ð70JOC0401Ł[
O i, Na, C6H6
O ii, RCOCl O
O-THP
iii, C6H6, AcOH, 80 °C n-C6H13
Cl + n-C6H13 (358)
O-THP 85%
Ph Ph
O
S S O
i–iv
+ Cl (359)
72%
TMS TMS
Cl Cl
i, LiOCEt3
O OH Cl O
B ii, H2O2, NaOH
+ MeO (361)
Cl 70%
O O
Ph
TMS O
AlMe3, –45 °C
HO
(362)
TMS 88%
Ph
OMs
Copyright # 1995, Elsevier Ltd. All R ights Reserved Comprehensive Organic Functional Group Transformations
3.06
Ketones Bearing an a,b-Aryl or
-Hetaryl Substituent
DARYL S. WALTER
University of Nottingham, UK
2[95[0 GENERAL METHODS 167
2[95[0[0 FriedelÐCrafts Acylations 167
2[95[0[0[0 Reactions with acyl halides 167
2[95[0[0[1 Reactions with carboxylic acids and anhydrides 179
2[95[0[0[2 Reactions with miscellaneous acylatin` a`ents 170
2[95[0[0[3 The Houben!Hoesch synthesis 171
2[95[0[0[4 Reactions with other acyl cation equivalents 172
2[95[0[1 Electrophilic Acylations of Or`anometallic Species 173
2[95[0[1[0 Acylations of or`anolithium rea`ents 173
2[95[0[1[1 Acylations of Gri`nard rea`ents 174
2[95[0[1[2 Acylations of or`anocopper rea`ents 175
2[95[0[1[3 Acylations of or`anotin rea`ents 176
2[95[0[1[4 Acylations of or`anozinc rea`ents 177
2[95[0[1[5 Acylations of miscellaneous or`anometallic rea`ents 178
2[95[0[2 Aryl Ketones by Carbonylative Cross!couplin` Reactions 178
2[95[0[3 Acyl Anion Equivalents in Aromatic Ketone Synthesis 180
2[95[0[3[0 1!Alkyl!0\2!dithianes 180
2[95[0[3[1 Protected cyanohydrins 181
2[95[0[3[2 Acyl radicals 181
2[95[0[3[3 Miscellaneous acyl anion equivalents 182
2[95[0[4 Oxidation 182
2[95[0[4[0 Oxidations of benzylic methylene `roups 182
2[95[0[4[1 Oxidations of secondary benzylic alcohols 183
2[95[0[4[2 Oxidative cleava`es of double bonds 183
2[95[1 PHENYL KETONES AND SUBSTITUTED ANALOGUES 184
2[95[1[0 Phenyl Ketones 184
2[95[1[1 Monoalkyl Phenyl Ketones 184
2[95[1[2 Dialkyl! and Polyalkylphenyl Ketones 185
2[95[1[3 Halophenyl Ketones 185
2[95[1[4 Phenolic Ketones 185
2[95[1[5 Alkoxyaryl Ketones 187
2[95[1[6 Thiophenyl Ketones 188
2[95[1[7 N!Substituted Phenyl Ketones 188
2[95[1[8 Other Substituents 299
2[95[2 POLYCYCLIC ARYL KETONES 299
2[95[2[0 Naphthyl Ketones 299
2[95[2[1 Anthryl Ketones 290
2[95[2[2 Phenanthryl Ketones 290
2[95[2[3 Other Polycyclic Aryl Ketones 291
2[95[3 HETARYL KETONES 291
2[95[3[0 Furanyl Ketones 291
2[95[3[1 Benzofuranyl Ketones 293
2[95[3[2 Ketothiophenes 294
166
167 Ketones With an a\b!Aryl or !Hetaryl
2[95[3[3 Benzothiophenyl Ketones 295
2[95[3[4 Pyrrolic Ketones 295
2[95[3[5 Ketoindoles 298
2[95[3[6 Pyridyl Ketones 209
2[95[3[7 Ketones Derived from Imidazoles\ Thiazoles and Oxazoles 200
Cl O O OH
TiCl4
O OH + (1)
O O CH2Cl2, –78 °C
MeO O
O O
MeO
Reactions requiring molar quantities of catalyst require workup procedures to decompose prod!
uct complexes and the catalyst is consequently not usually recovered[ Reactive aromatics "e[g[\
thiophenes# can be acylated over sulfonated polystyrene resins ð44USP1600303Ł\ and benzoyl chlorides
will yield benzophenones on exposure to arenes and the solid Na_on!H catalyst ð67S561Ł[
Ammonium salts of Keggin!type heteropolyacids ð81CL0876Ł have also shown promise as solid!
phase FriedelÐCrafts catalysts[ These heterogeneous procedures allow for easy recovery of both the
products and the catalyst[
Acylations of active aromatic nuclei such as aryl ethers\ polynuclear arenes\ and thiophene with
acyl halides do not always require a catalyst but trace amounts of a variety of metallic and non!
metallic catalysts greatly increase the reactions rates and the yields ð61S422Ł[ The most frequently
employed catalysts of this ilk are ferric chloride "Equation "1## ð74BSB786Ł\ iodine "Equation "2##
ð37JA0536\ 42JA634Ł\ zinc chloride "Equation "3## ð43JA4358Ł and iron "Equation "4## ð69MI 295!90Ł[
Attractive aspects of these methods are the ease of product puri_cation and low costs[ Relatively
high reaction temperatures are required and aromatic acid chlorides generally give better yields
than aliphatic ones[
5 equiv. 1 equiv.
O O
MeO
I2, reflux, 8 h
+ Cl (3)
89%
MeO
OMe
O O
ZnCl2 (0.02 equiv.), reflux But
+ Cl (4)
66%
OMe
But
OMe O O
Fe (0.01 equiv.), 85 °C
+ Cl (5)
90%
MeO
Catalytic quantities "ca[ 0)# of tri~uoromethanesulfonic acid e}ectively increase rates and yields
in FriedelÐCrafts acylations with acyl halides ð61AG"E#299Ł and presumably proceed via the inter!
mediacy of labile tri~uoromethanesulfonic!carboxylic anhydrides[ This method allows for acylations
with pivaloyl chloride without the decarbonylation and t!butylation complications mentioned earlier
"Equation "5##[ In contrast to all of the above catalytic methods\ acylations of aryl ethers are
promoted e}ectively by small quantities of diphenylboryl hexachloroantimonate ð75CL054Ł at room
temperature in dichloromethane solutions "Equation "6##[
OMe O
O CF3SO3H (cat.), 154 °C, 12 h
+ But (6)
But Cl 54%
MeO
179 Ketones With an a\b!Aryl or !Hetaryl
OMe O
O Ph2BSbCl6 (cat.), CH2Cl2, RT, 24 h
+ Bun (7)
Bun Cl 88%
MeO
O
OH O BF3, 0–25 °C, 48 h OH
+ (8)
OH 90%
OMe
OMe
OH OH O
O BF3, HF, p-xylene, 70 °C HO
HO OH
+ ( )18 (9)
HO ( )18 90%
HO
Toluene and xylene can be acylated with fatty acids in the presence of a Y!faujasite!type zeolite
after exchange with Ce2¦ cations ð75JOC1017Ł[ The shape!selectivity imposed by the dimensions of
the zeolite channels results in no acylation with acetic acid and increasing ketone yields with higher
homologs\ and maximum yields using dodecanoic and palmitic acids with toluene and p!xylene
respectively[ Carboxylic acids and phosphorus pentachloride ð60AP"293#432\ 77CB006Ł\ phosphorus
oxychloride ð72CI"L#368Ł\ and sulfonyl chloride ð73JOC3115Ł provide alternative acylation conditions\
but a Lewis acid is usually required and the reactions probably proceed via the corresponding acyl
chlorides[
Along with acyl chlorides\ acid anhydrides are the most popular acylating species in the FriedelÐ
Crafts ketone synthesis\ particularly when using reactive aromatic substrates[ Used in conjunction
with stoichiometric quantities of catalysts such as aluminum chloride\ ferric chloride\ zinc chloride\
boron tri~uoride and tri~uoroacetic acid they provide a convenient route to ketones[ However\
practical considerations such as the thermal instability and moisture sensitivity of many anhydrides
has largely limited the reactions to acetylation "for which this method is particularly good#\ pro!
panoylation and butanoylation[ The in situ preparation of highly reactive mixed anhydrides avoids
these problems and provides a useful route to ketones based on the corresponding carboxylic
acids[ Carboxylic dihalophosphoric anhydrides ð70CB815Ł and acyl tri~uoroacetates ð68S292\ 79S028\
77BCJ344Ł have both found some use "Equations "09# and "00##[
OMe MeO
O TFAA, MeCN, 85% H3PO4
+ (10)
OH 66%
O
TFAA = trifluoroacetic anhydride
General Methods 170
O
O
2-PyOTf, TFA
+ OH (11)
99%
As with the reactions of acyl halides\ carboxylic acid anhydrides can serve as useful acylating
agents for active aromatic nuclei in the presence of little or no catalyst ð61S422Ł\ but usually under
rather drastic conditions[ However\ later work\ mostly by Mukaiyama and his co!workers\ has seen
the development of substoichiometric catalysts which provide aromatic ketones using anhydrides
under very mild experimental conditions[ Diphenylboryl hexachloroantimonate ð75CL054Ł\ gallium
chloride:silver perchlorate "Equation "01## ð80CL0948\ 80S0105Ł\ antimony chloride:lithium per!
chlorate ð81CL324Ł and lanthanide tri~uoromethanesulfonates ð82CC0046Ł all provide high yields of
ketones with electron!rich aromatic substrates\ and with one exception\ at room temperature in
dichloromethane[ Carboxylic acids "or their trimethylsilyl esters# and p!tri~uoromethylbenzoic
anhydride in the presence of a silicon tetrachloride:silver perchlorate catalyst system constitute an
e.cient and mild route to the corresponding ketones "Equation "02## ð81CL0640\ 82BCJ2618Ł[
OMe
GaCl3 (10 mol%)/AgClO4
O
CH2Cl2, RT
+ (C5H11CO)2O C5H11 (12)
91%
MeO
OMe O O
SiCl4 (20 mol%)/AgClO4
CH2Cl2, RT
+ O-TMS (13)
100%
MeO
O AlCl3, reflux
+ ( )15 (14)
83% ( )15
O
O
O
OMe SbCl5/Ph2BCl, NaHCO3 (aq.)
O CH2Cl2, RT
MeO
+ (15)
O 71%
MeO
OMe
171 Ketones With an a\b!Aryl or !Hetaryl
Seleno esters provide a useful alternative to classical FriedelÐCrafts acylating agents and give
good to high yields of ketones using active aromatic substrates "e[g[\ anisole\ furan#\ and the
crystalline complex of copper"I# tri~ate and benzene ð"CuOTf#1PhHŁ as catalyst ð79JA759Ł[ The tri~ic
acid generated can be scavenged by inclusion of calcium carbonate in the reaction mixture[
Some useful reactive reagents for acetylation and tri~uoroacetylation of aromatic systems include
acetylmethanesulfonate ð78SL43Ł\ tri~uoroacetyl tri~ate ð68JOC202Ł and 1!"tri~uoroacetoxy#pyridine
ð89CL672Ł[ The _rst two reagents require no catalysts for e.cient reaction\ and the latter compound
produces\ in the presence of aluminum trichloride\ the tri~uoroacetyl derivative of benzene in
moderate yield at 9>C in dichloromethane "Equation "05##[ In a similar vein\ oxocarbonium hexa!
~uoroantimonates are equally reactive and provide benzene derived ketones in good yields with no
need for catalysts "Equation "06## ð52JA0217\ 53JA1192Ł[
O
O AlCl3
+ CF3 (16)
N O CF3 53%
O
O benzene, warm
SbF6–
+ (17)
+
93%
Finally\ ketones behave as internal anhydrides and will acylate aromatic compounds in the
presence of aluminum trichloride and some other catalysts ðB!53MI 295!90\ B!62MI 295!91Ł[ The varied
outcomes of such reactions have led to little practical application[
OH OH
HO OH CN HO OH
ZnCl2, HCl, Et2O
+ (18)
63%
OH OH O
NC
H
N N Me O Me
N
H2SO4 (conc.) MeO
(19)
CHCl3
N
MeO MeO H
OMe
General Methods 172
NC CN NH2 O
AlCl3, toluene
N (20)
N 34%
H N
N
O
H CCl3 i, AlCl3
N ii, H2O
+ O (21)
O 98%
N
H
Some sulfur!based functional groups which serve as alternative masked acylating agents include
1!substituted 0\2!benzoxathiolium tetra~uoroborates ð76S200Ł\ bisphenylthionium ions ð76T0736Ł
and acyl sulfones ð73JA1358Ł[ The former reagents add e}ectively to active aromatic substrates to
provide intermediate benzoxathioles which are easily hydrolysed to the corresponding ketones[ The
reactions proceed under mild conditions and o}er the possibility of introducing tertiary acyl groups
"Equation "11##[ Bisphenylthionium ions are generated by the action of dimethyl"methylthio#
sulfonium ~uoroborate "dmtsf# or silver tri~ate on tris"phenylthio#alkanes and\ through sub!
sequent hydrolysis of the thioacetals obtained\ provide a useful method for intramolecular acylation
"Scheme 0#[ Intramolecular acylations are also possible with reactive acyl sulfones\ generated in situ
by the action of Lewis acids "BCl2 and TiCl3# on protected alkoxy!bis"sulfonyl# derivatives\ and lead
directly to the required ketone "Equation "12##[ These three methods are signi_cant in that the
starting materials are easily prepared and are inert to various other functional group manipulations\
thus allowing for selective unmasking of the active acylation species as required[
OMe OMe O
S i, pyridine, MeCN, 50 °C
ii, HgO, THF, HBF4 (aq.), RT
+ + But But (22)
O BF4– 60%
MeO MeO
Scheme 1
O2S
O O
TMS
S TiCl4, CH2Cl2, –10 °C to 0 °C
O2 (23)
68%
173 Ketones With an a\b!Aryl or !Hetaryl
2[95[0[1 Electrophilic Acylations of Organometallic Species
For a long time the synthesis of ketones by acylation of nonstabilised organometallic species
with carboxylic acid derivatives was a problematic process[ The fact that the required ketone was
often considerably more reactive than the usually weakly electrophilic substrate resulted in over!
addition and the formation of alcohols[ Relatively recent developments have largely solved such
problems\ and various single step methodologies are now available ð80COS"0#286Ł[ The aromatic
component of the ketone target can be introduced as a nucleophilic or electrophilic moiety
"Scheme 1#\ and consequently allows for considerable ~exibility in synthetic design\ often providing
more practical or complementary alternatives to methods such as the FriedelÐCrafts acylation[ The
ease of preparation of aromatic anions is central to the importance of these methods[
O O O
ArM + + RM
X R Ar R Ar X
Scheme 2
O O
MeO Li
–78 °C MeO
+ HO OH OH (25)
83%
MeO NHSO2Ph NHSO2Ph
MeO
Acylations of organolithium species by simple carboxylic acid derivatives are generally not widely
applicable\ due largely to the poor stability of the so!formed tetrahedral intermediates\ but examples
have been reported for a number of such substrates[ Thus\ acid chlorides "Equation "15##
ð71JOC0474Ł\ esters ð75JOC840Ł\ lactones "Equation "16## ð72JA6533\ 73CC429Ł\ and amides "Equation
"17## ð73TL700Ł have all been utilised in this manner[
O
N N O
BuLi O
+ Cl (26)
O
MeO
OMe
General Methods 174
OMe O OMe O
MeO2C OH
O
hydrolysis
+ O OMe (27)
O 60%
Li
OMe OMe O OMe OMe O
O
Li O
+ (28)
N
The best acylating agents to date are the N!methoxy!N!methylamides developed by Weinreb
ð70TL2704Ł[ These species are readily available from the corresponding carboxylic acids\ are tolerant
of many reaction conditions\ and selectively yield the desired ketone products even in the presence
of excess organolithium reagent[ The product speci_city of these compounds is due to the exceptional
stability of the tetrahedral intermediate which e}ectively masks the ketone product from further
reaction[ The aromatic moiety may be incorporated into either the nucleophilic ð76JOC1504Ł or
electrophilic ð70TL2704Ł substrate\ and can also be applied in an intramolecular fashion as dem!
onstrated in a recent approach to benzocyclobutenones starting from iodo!substituted aromatic
Weinreb amides "Equation "18## ð81TL4320Ł[
Me
MeO
MeO N ButLi, THF, –78 °C
OMe (29)
67% MeO
O O
MeO I
O O
MgBr
VCl3, CH2Cl2 OEt
+ Cl
OEt (30)
76%
O O
O
MgBr O Fe(acac)3 (3 mol%), THF
+ (31)
Cl 55%
MeO
OMe
Some Grignard reagents will react with aryl esters in the presence of triethylamine to give the
desired ketones ð79S766Ł[ This method relies on masking of the intermediate ketone by basic
enolisation\ and is consequently highly substrate dependent[ As in the previous section\ Weinreb
amides ð70TL2704Ł are good acylating agents for organomagnesium compounds but a number of
175 Ketones With an a\b!Aryl or !Hetaryl
other acid derivatives rival their success in such transformations[ Some of the best such substrates
are the S!"1!pyridyl# thioates developed by Mukaiyama ð62JA3652\ 63BCJ0666Ł[ Derived from the
corresponding acids or acid chlorides\ these compounds do not stabilise tetrahedral intermediates
but\ rather\ provide highly reactive species by coordination to the divalent magnesium ion\ which
are selectively attacked in preference to other ketone functionality "Equation "21## or ketone
intermediates[ In a similar vein\ esters derived from 7!hydroxyquinoline ð51JA3788Ł\ 1!hydroxy!2!
methylpyrazine "Equation "22## ð66CL534Ł\ 1!pyridyl ketone oximes "Equation "23## ð75CL338Ł and
N\N!diphenyl!p!methoxyphenylchloromethyleneiminium chloride "Equation "24## ð71TL4948Ł have
all shown some utility in aromatic ketone synthesis\ as have anhydrides ð37JOC481Ł\ mixed an!
hydrides of phosphorus ð67SC48Ł and acylimidazoles ð51LA"544#89Ł[
O O
S PhMgBr, THF, 0 °C Ph
(32)
O N O
O
N
O PhMgBr
(33)
O N 79%
O N
PhMgBr O
C15H31 O N (34)
85% C15H31 Ph
Ph
O N+
Ph
PhMgBr Ph
O Cl– (35)
66% O
OMe
Finally\ aryl Grignard reagents can add to nitriles to give iminyl intermediates which are easily
hydrolysed to the corresponding ketones on workup ð58JA4775\ 61JOC2258Ł[ Mild Lewis acids such
as LiClO3 ð64JOM"88#30Ł and TMS!Cl "Equation "25## ð80TL5620Ł often improve the e.ciency of
this transformation[
i, TMS-Cl O
MgBr O
O ii, H3O+ O-TBDMS
+ NC O-TBDMS (36)
96%
TBDMS = t-butyldimethylsilyl
CN CN O
O DME, 0 °C
Cu
+ Ph (37)
Ph Cl 71%
Alternatives to acid chlorides include thiol esters "Equation "27## ð79TL1902Ł\ and 1!pyridyl esters
"Equation "28## ð72JOC1597Ł[ The latter are particularly useful as their high reactivity promotes
reaction with the intermediate lithium alkyl "1!pyridyloxy# cuprate complex\ and hence allows for
e}ective reaction using a single equivalent of dialkyl cuprate[ The conditions also tolerate functional
groups such as bromide\ ketone and ester in the pyridyl ester moiety[
SPh Ph
Ph2MgCuX, Et2O, THF
N O N O (38)
O PPh3 O PPh3
CO2NB CO2NB
O N THF, –78 °C O
+ But2CuLi (1 equiv.) (39)
Ph O 74% Ph But
The uneconomical nature of nonstoichiometric dialkyl cuprates and the thermal instability of
s! and t!alkylcuprates ð58JA3760Ł has led to the development of mixed cuprates with only a single
transferable ligand[ The most successful nontransferable ligands for acylation of cuprates have been
various heteroalkyls[ Phenylthio and t!butoxide "Equation "39## ligands give good to excellent
results ð62TL0704\ 62JA6677Ł at −67>C\ and diphenyl "Equation "30## and dicyclohexyl phosphido
ligands show similar utility at room temperature ð71JA4713\ 73JOC0008Ł[ More recently\ Knochel and
his co!workers have developed a new class of organocopper reagents "RCu"CN#ZnI# which are
easily prepared from alkyl iodides[ These reagents are stable up to 9>C\ they have one transferable
group and furthermore they tolerate a wide range of functionality "Equation "31## ð77JOC1289Ł[
O O
THF, –78 °C
Cl + But(ButO)CuLi But (40)
82%
O O
Et2O, 0 °C
Cl + ButCu(PPh2)Li But (41)
80%
O
O O O
O i, ii, iii
O (42)
I 80%
O
O
O PhCH2Pd(PPh3)2Cl O
+ Ph4Sn (43)
Cl 76% Ph
O O
PhCH2Pd(PPh3)2Cl
Cl + Me4Sn (44)
100%
NC NC
O PhCH2Pd(PPh3)2Cl O
+ Me4Sn (45)
But Cl 82% But
O Cl O
PhCH2Pd(PPh3)2Cl
+ Me4Sn (46)
86%
CHO CHO
O O
(dppf)PdCl2, THF, Et2O
Cl + Bun2Zn (47)
82%
General Methods 178
O
ZnCl O Pd(PPh3)4, THF
+ Ph (48)
Ph Cl 95%
Cl
Cl
O O
Pd(PPh3)4 (1 mol%), THF
Cl + Na+ –BPh4 Ph (50)
76%
O2N O2N
O
Cl O
NiCl2 (10 mol%), Zn, DMF Cl
+ I (51)
N
81%
OMe
transition-metal catalyst O
ArX + RM (52)
CO atmosphere Ar R
Palladium catalysts give access to the most general methods for the above!mentioned trans!
formations[ Tanaka ð68TL1590\ 70BCJ526Ł _rst showed that aryl halides and organotin compounds
give ketones in the presence of C5H4PdI"PPh2#1 and carbon monoxide[ However\ this method
requires high CO pressures and HMPA as cosolvent\ two factors which detract from this reagent
189 Ketones With an a\b!Aryl or !Hetaryl
combination[ Aryl diazonium salts react with tetramethyltin and carbon monoxide\ using palladium
diacetate as catalyst\ to give good yields of acyl arenes ð71CL24Ł[ This method is compatible with
various aryl substituents "i[e[\ Me\ Cl\ Br\ I\ NO1^ Equation "42## but does not work as well with
other tetralkyltin compounds and again requires high CO pressures[
O
N2+ BF4–
Pd(OAc)2 (2 mol%), CO
+ Me4Sn (53)
85%
O2N
O2N
Coupling reactions of aryl iodides with alkyl! or benzylzinc compounds and using tetra!
kis"triphenylphosphine#palladium gives the desired ketones in moderate to good yield under an
atmospheric pressure of carbon monoxide "Equation "43## ð72TL2758Ł[ Aryl tri~ates\ which are
readily available from phenols\ react with organostannanes in the presence of carbon monoxide
"0 atm#\ dichloroð0\0!bis"diphenylphosphino#ferroceneŁpalladium"II#\ and lithium chloride to a}ord
a variety of aryl ketones\ again in variable yields ð77JA0446Ł[ Many functional groups are tolerated
by this method "e[g[\ Equation "44##\ but strong electron!withdrawing groups on the organo!
stannanes should be avoided[ Unsymmetrical diaryl and aryl!hetaryl ketones are conveniently
accessed by cross!coupling reactions of organo~uorosilanes with aryl halides in the presence of
carbon monoxide "0 atm#\ potassium ~uoride and "h2!C2H4PdCl#1 ð78CL1938\ 81T1002Ł[ The reaction
conditions tolerate reactive functional groups such as esters\ ketones\ aldehydes "Equation "45## and
nitriles[
O
Pd(PPh3)4 (1 mol%), CO (1 atm)
I
Zn–Cu, THF
+ I (54)
91%
O
OTf
PdCl2(dppf) (4 mol%), CO (1 atm)
LiCl, DMF
+ PhSnMe3 (55)
78%
OAc
OAc
(η3-C3H5PdCl)2, CO (1 atm)
KF, DMI
+ S
(56)
S Si(Et)F2 72% CHO
I CHO
O
Unsymmetrical biaryl ketones and alkyl aryl ketones are available by palladium!catalysed
"PdCl1"PPh2#1# carbonylative cross!coupling of 8!alkyl!8!BBN derivatives or arylboronic acids with
iodoarenes as described by Suzuki and his co!workers ð80BCJ0888\ 80TL5812\ 82TL6484Ł[ These reactions
"e[g[\ Equation "46## generally give good yields of ketones and the conditions used are intrinsically
non!intrusive to a range of functionality[ Sodium tetraphenylborate ð77JOM"234#286Ł and aryl!
aluminum compounds ð74TL3708Ł undergo carbonylative cross!coupling with alkyl! and aryliodides
respectively[ The former requires a platinum catalyst and high CO pressure\ whereas the latter
proceeds at atmospheric pressure with PdCl1"MeCN#1[ The nature of the organometallic species
somewhat limits the synthetic value of these methods[ Rhodium"I# catalysts have found some use
in the carbonylation of arylmercury ð79JOC2739\ 71IZV110Ł and arylbismuth reagents ð81CC342Ł[
Isocyanides\ which are isoelectronic with carbon monoxide\ can be utilised in palladium!catalysed
iminocarbonylative cross!coupling reactions to yield imines which are readily hydrolysed to the
corresponding aryl ketones[ Both organotin ð74TL2352\ 75BCJ566\ 75CL0086Ł and 8!alkyl!8!BBN "8!
BBN8!borabicycloð2[2[0Łnonyl# derivatives ð81TL3354Ł can be utilised in this manner[ The former
react with imidoyl chlorides and Pd"PPh2#3\ whereas the latter combine with t!butylisocyanide and
aryl halides in the presence of Pd"PPh2#3 and K2PO3 to give good yields of functionalised aryl alkyl
ketones after hydrolytic workup "Equation "47##[
General Methods 180
F CO2Me
B(OH)2 CO2Me PdCl2(PPh3)2 (3 mol%)
CO (1 atm), K2CO3, anisole
+ (57)
76%
F I
O
O
I O O
i, ii
+ B (58)
O 89%
O
MOM-O
MOM-O
i, Pd(PPh3)4 (5 mol%), ButNC, K3PO4, dioxane, THF; ii, 2M HCl
MOM = methoxymethyl
Scheme 3
2[95[0[3[0 1!Alkyl!0\2!dithianes
1!Alkyl!0\2!dithianes\ which are derived from the corresponding aldehydes or by alkylation of
1!lithio!0\2!dithiane\ are readily lithiated\ and the resulting anions can then be alkylated with a
variety of electrophiles to give masked ketones which are henceforth unveiled on hydrolysis ð66S246Ł[
Similarly\ 1!aryl!0\2!dithianes are readily prepared from benzaldehyde and its derivatives or from
other aryl aldehydes ð66OS"45#7Ł[ Examples of metallation and electrophilic alkylation of such com!
pounds are found in an approach to lignan lactones "Equation "48## ð67JOC874Ł\ the synthesis of
2!acetylindole ð61HCA64Ł\ and in studies of conjugate additions to a!alkylidene!g!butyrolactones
ð74TL2916Ł and to a\b!unsaturated esters ð74TL2920Ł[ Alkylations with alkyl halides\ epoxides "Equa!
tion "59## and carbonyl compounds are all relatively high yielding ð66S246Ł[ Conversely\ 1!aryl!
1!lithio!0\2!dithianes have been successfully arylated using "h5!alkylbenzene# Cr"CO#2 complexes
"Equation "50## ð72OM356Ł[
O
H
O
O
i, 2-butenolide
S S ii, 3,4,5-trimethoxybenzyl chloride O
O H O (59)
Li iii, HgO–BF3, THF, H2O
O
MeO OMe
OMe
O-MOM O-MOM
i, BunLi
(60)
S O MOM-O
MOM-O ii, S S
S OH
181 Ketones With an a\b!Aryl or !Hetaryl
But
But But
Ar Li
S S + Ar
Ar + (61)
80% S S
S S
(OC)3Cr
63 : 37
Ar = NMe2
O-TMS TMS-O CN
i, LDA
CN (62)
O
ii, O
86%
i, LDA
O-TMS O O O
ii, Br
O
CN O (63)
iii, [(C2H5)3NH]F
60%
O
O OMe
Bun3SnH, AIBN O
SePh benzene, ∆
(65)
OMe 84%
O
O
Pd(PPh3)4, ZnCl2 MeO
Na[BuiCOFe(CO)3L] + MeO (67)
69% Bui
I
O
2[95[0[4 Oxidation
Ketones are readily prepared by oxidative methods\ and the extra facility imparted to such
procedures by the proximity of aromatic groups often makes oxidation a viable route to the desired
aryl and hetaryl ketones[ Benzylic methylene carbon atoms\ secondary alcohols and alkenes can all
be e.ciently transformed into ketones in this manner[
Ph Ph
H H
AcO CrO3, NaOH (0.5N) AcO O
HOAc (80%)
(68)
70%
MeO MeO
MeO MeO
O O
NMe NMe
O air, EtOH O
OMe OMe (70)
OMe O 63% MeO O O
OMe OMe
O O
O
O OEt OsO4, NaIO4, Et2O, H2O
(71)
O 65%
MeO MeO CO2H
R2 R2 R2
R1
R3 R
R1
R1 O O O R O R
O R3 O R3
(1) (2) (3) (4) (5) (6)
OH
OH
O O ZnCl2, 140 °C
+ (72)
O 70% OH
OH
O
OH
O
TiCl4
(73)
O 96%
O
O O
MeO O MeO OH
O
OMe OH O
OMe O
BF3
(75)
86%
OMe
OMe
O
O O
O
N O AlCl3
N OH (76)
49%
OH O
O Ph
HF Ph
(77)
O 76%
The Fries rearrangement can also be accomplished in the absence of a catalyst by irradiation with
UV light[ Known as the photo!Fries rearrangement ð56CRV488Ł\ both o! and p!adducts can be
prepared and some success has been achieved with deactivated aromatic substrates[ Two examples
are shown in Equations "67# and "68# ð51JOC1182\ 75H"13#1400Ł[
187 Ketones With an a\b!Aryl or !Hetaryl
O
OH O
O
hν, benzene
Cl (78)
72%
Cl
But
But
O OH O
Ph O O
O hν, benzene
Ph
O (79)
65%
O
MeO OMe
R1 O OMe
O R O R2 O R
(7) (8) (9) (10) (11) (12)
OMe H
O O O
BF3
+ (80)
HO 73%
MeO OMe MeO OMe
Substitution of groups such as i!propyl and t!butyl by the acyl species occurs in some cases\
particularly as the substitution of the aromatic substrate is increased[
Organolithium derivatives of aryl ethers can be prepared by metalÐhalide exchange reactions or
by ortho!metallations using the O!alkyl substituents as directing groups ð89CRV768Ł[ Acylations of
such species or of compounds derived therefrom provide routes to ketones which would not be
accessible by FriedelÐCrafts methodology[ For instance\ Equation "70# illustrates an example where
o!lithiated anisole is acylated regioselectively to give the ketone product which is usually only
Phenyl Ketones and Analo`ues 188
produced in relatively small amounts in the FriedelÐCrafts reaction[ Alkoxy aromatic substituents
are generally quite inert and compatible with most general methods[
O
+ BnO OMe (81)
Li N 90% OBn
OMe Me OMe O
O
O AlCl3
+ + (83)
N N
Cl N
R R O
R
R = CONHMe >98 : <2 96%
R = COCF3 10 : 87 13%
Ph
O
O H
O N
O
Ph
H N AlCl3
H (84)
60%
N
N
Ph
O Ph
O
Nitro!arenes form very tight deactivated complexes with Lewis acids and generally do not undergo
FriedelÐCrafts acylations[ However\ electron!donating substituents can sometimes override this
299 Ketones With an a\b!Aryl or !Hetaryl
e}ect\ and the use of an AlCl2:DMF complex provides an isolated example of the FriedelÐCrafts
acylation of nitrobenzene itself ð89JOC2850Ł[ In an analogous fashion to the Fries!rearrangement\
aryl amides can undergo both Lewis acid catalysed and photochemical rearrangement to the
corresponding acyl anilines in good yields "Equations "74# to "76## ð65TL2106\ 73IJC"B#052\ 75SC374Ł[
O Cl
H NH2 O Cl
N
BiCl3
(85)
80%
OMe
OMe
O OH O
Cl
B(OH)3, H2SO4, SO3
(86)
63%
N
O
H NH2 O
H NH2
N Ph hν, H2O
Ph (87)
O O2N
O2N O
Amines\ amides and urethanes can serve as directing groups in o!lithiation reactions ð89CRV768Ł\
and nitro substitution is tolerated by Stille reaction conditions ð75AG"E#497Ł[ Both methods conse!
quently provide alternative direct routes to N!substituted phenyl ketones\ although examples in the
literature are comparatively rare at present[
O R
OMe O FeCl3 (cat.)
+ OMe (88)
R Cl 66–90%
O CF3
CF3CO2Tf, base
(90)
81%
O Ph
O I2 (cat.)
+ (91)
Ph Cl 68%
O O R
(13) (14)
O R
O
O (CuOTf)2Ph
+ O (92)
( )5
O ( )5 SeMe 100%
O O
TBDMS-O TBDMS-O
Hg(OCOCF3)2, MeCN
(93)
O H 65%
O H
SBut
O O
( )4
O
SnCl4, benzene
MeO
+ (n-C5H11CO)2O MeO ( )4 + (94)
O O
21% MeO
O O O O
O
62 : 38
Acylations of lithiated furans are of considerable contemporary importance and allow for regio!
selective and often high yielding ketone syntheses[ Furans can be lithiated selectively at the 1!
position using alkyllithium reagents\ and at the 1! or 2!position by lithiumÐhalogen exchange[
Furthermore\ lithiation of the 2!position is possible using various functional groups at the 1!
position to direct the metallations ð71JCS"P0#0232Ł[ A range of electrophiles including Weinreb amides
"Equation "84## ð82TL1354Ł\ dimethylamides ð78SC676Ł\ anhydrides and acids ð58JHC030\ 81AG"E#0924Ł
have proved useful\ and transmetallations of the lithium species to the corresponding organocuprates
ð68TL3466Ł or organomanganates ð81TL4134Ł allow for e}ective acylations with acid chlorides[
Stannylated furans and acid chlorides in the presence of palladium"9# catalysts undergo extremely
e}ective coupling reactions and constitute a very mild ketone synthesis ð80ACS803\ 80OM255\ 80S132Ł[
2\3!Distannyl furans can similarly be mono!acylated and subsequently arylated or vinylated to
provide furanyl ketones which could otherwise prove somewhat di.cult to access "Equation "85##
ð81CC545Ł[ Carbonylative cross!coupling reactions of stannyl furans with allyl chlorides\ again in
the presence of a palladium catalyst\ also provide the corresponding ketones in high yields ð73JA3722Ł
and have been applied to the synthesis of relatively complex ketones "Equation "86## ð77TL0062Ł[
An obvious aspect of such reactions is the use of furanyl acid chlorides as the electrophilic partners
in such palladium!catalysed reactions[ A number of such examples are found in the various catalysed
and uncatalysed reactions of other organometallic species "e[g[\ Equation "87## ð56T786\ 71CL0448\
72TL1340\ 78JOC4191\ 81TL4134Ł[ Anions of cyanohydrins derived from furanyl aldehydes have found
some use as umpoled synthons for ketone synthesis ð68CB1934\ 73SC632Ł\ and the additions of organo!
metallic reagents to furanyl aldehydes with subsequent oxidations of the resulting alcohols is a fairly
popular route to the corresponding ketones[ Oxidations of furan methanols using chromium reagents
ð73JA1004\ 75JA0945Ł\ t!butyl hydroperoxide ð82TL6978Ł\ Swern conditions ð89JCS"P0#1566Ł\ barium
manganate "Equation "88## ð74JA4108Ł and manganese dioxide ð76JA2870Ł have all been reported[
Me
O O
Li + N (95)
O OMe 79% O
O O O
O
O O2N
i, Cl , PdCl2(PPh3)2
Bu3Sn SnBu3 O
(96)
Br
O ii, , Pd(PPh3)4
O2N
O
293 Ketones With an a\b!Aryl or !Hetaryl
MeO OMe
SnBu3
Pd(acac)2, PPh3, CO (1 atm)
+
Cl TMS O
MeO OMe
O
(97)
O
TMS
O
O Zn, CuCN(LiCl)2, THF
Cl
O + But O O (98)
But O I 81%
O O
BaMnO4, CH2Cl2
OBn OBn (99)
O 80% O
OH O-TBDMS O O-TBDMS
Ph
O
O SnCl2
+ (100)
O Cl 60%
O TiCl4 But
TMS + (101)
O But Cl 75% O O
Hetaryl Ketones 294
OMe
OMe OEt
O BF3•OEt2
OEt + (102)
HO 88% O O
O O
O
2[95[3[2 Ketothiophenes
Thiophenes have considerable aromatic character but they are also considerably more reactive
toward electrophiles than is benzene[ Consequently FriedelÐCrafts acylations can be e}ected under
various conditions ðB!53MI 295!90Ł[ Acid chlorides\ anhydrides and carboxylic acids are the most
commonly used electrophiles\ and the most popular catalysts are aluminum trichloride "e[g[\
ð82ACS176Ł# and tin tetrachloride "Equation "092## "e[g[\ ð73JOC1211\ 73TL4328Ł# in the case of acid
chlorides^ pyridyltri~ate:TFA ð68S292\ 79S028\ 77BCJ344Ł and protic acids such as ppa for carboxylic
acids ð79JHC76Ł^ and iodine ð61S422Ł boron tri~uoride ð37JA756Ł\ perchloric acid ð60HCA242Ł and
phosphoric acid ð44OSC"2#03Ł with the corresponding anhydrides[ Thiophene has been similarly
acylated in high yield using selenoesters and a copper catalyst ð79JA759\ 74T3710Ł\ and benzoylated
with equal facility using trichloromethylbenzene and aluminum trichloride ð80S211Ł[ Fries!
rearrangements involving substituted thiophenes are also possible but not particularly general
"Equation "093## ð75JCS"P0#496Ł[ Acylations under FriedelÐCrafts conditions are highly selective and
give the 1!substituted products exclusively[ 1!Substituted thiophenes react with similar dis!
criminations to give the 1\4!products\ and 1\4!disubstituted thiophenes are acylated at the 2! or
3!position as dictated by relative steric and electronic e}ects[ An exception to the latter occurs in
the case of 1\4!dihalothiophenes where the acylating species can substitute for either halogen
ð70JHC0234Ł[ Finally\ 2!substituted thiophenes react to give 1\2! and 2\4!disubstituted products in
distributions which are determined by the nature of the substituent[
O O SnCl4 Ph OMe
Ph + ( )6 S (103)
( )6 S Cl OMe CH2Cl2
O O
O
O HO
O AlCl3, HCl, CH2Cl2 OMe
OMe (104)
79%
O S
S
O
Thiophenes are readily metallated to produce reagents which can be acylated in high yield with
complete regioselectivity[ Thienyllithium compounds are by far the most popular of such species
and are readily prepared by halogenÐmetal exchange reactions using butyllithium "e[g[ ð81JHC136Ł#[
1!Lithiothiophenes can be prepared by the direct action of strong lithium bases "e[g[ ð80JOC3159Ł#\
and directed lithiations are a viable route to 2!lithio species ð89CRV768Ł[ The best general method
for the direct conversion of thienyllithiums into the corresponding ketones is by reaction with
Weinreb amides "Equation "094## ð80JOC1800\ 80JOC3159\ 80TL610\ 81JHC136Ł[
O Ph
+ OMe (105)
Li N 91% S
S
Ph Me O
1!Iodothiophenes and organoaluminum compounds have been converted into the corresponding
1!keto products by palladium!catalysed carbonylations ð74TL3708Ł\ and the related imino!
carbonylative cross!coupling with 8!alkyl!8!BBN derivatives "Equation "095## ð81TL3354Ł has also
been reported[ Furthermore\ 1!ethyldi~uorosilyl thiophene and aryl halides undergo similar pal!
ladium!catalysed carbonylative cross!coupling reactions to give diaryl ketones "Equation "096##
ð78CL1938\ 81T1002Ł[ All of these palladium!catalysed reactions are high yielding and provide an
extremely mild methodology for ketone synthesis[ Acid chlorides and other derivatives of thiophenyl
295 Ketones With an a\b!Aryl or !Hetaryl
carboxylic acids have been used as electrophiles in the acylations of various organometallic species
"Equation "097## ð65JCS"P0#638\ 76TL1942\ 81TL4134\ 82JOC4751Ł to produce the corresponding ketones[
i, Pd(PPh3)4 (5 mol%), K3PO4
9-BBN ii, H3O+
+ + ButNC (106)
S I 83% S
O
Me
MgBr
N +
S N + (108)
90% S
O N
O
Me
O
O O
ppa
OH (109)
72% O
S S
ppa = polyphosphoric acid
As is the case with thiophenes\ 1!lithio derivatives of benzothiophenes are readily prepared by
the action of butyllithium\ and they can be acylated successfully "e[g[ ð79TL1018\ 80TL1992Ł[
2!Lithiobenzothiophenes are not thermally stable and have only found limited use in ketone
synthesis[ However\ 2!aroylbenzothiophenes have been prepared in high yields by palladium!
catalysed carbonylative cross!coupling reactions of arylboronic acids with 2!iodo benzothiophene
"Equation "009## ð82TL6484Ł[
O
I CO (1 atm) Ph
PdCl2(PPh3)2 (3 mol%)
+ PhB(OH)2 (110)
K2CO3
S
S
O O
O
AlCl3
+ Cl (111)
55%
N N
H H
O
Selenoesters in the presence of copper catalysts are also an e}ective acylating combination
ð79JA759\ 74T3710Ł\ as are dimethylamino! ð74JMC0926Ł and morpholido amides "Equation "001##
ð66JOC3137\ 73JOC3192Ł in the presence of phosphorus oxychloride in what amounts to an extension
of VilsmeierÐHaack type formylations[ Although requiring subsequent hydrolysis to the ketone\ the
HoubenÐHoesch synthesis has found some utility "Equation "002## ð72JHC0454Ł as have reactions
using 0\2!benzoxathioyl ð82JCS"P0#162Ł and dialkoxycarbenium tetra~uoroborates ð78JHC0452Ł[
N!Alkyl and other N!protected pyrroles can often be acylated "and acetylated in particular# by simply
heating with acid chlorides ð74JMC0926Ł or active anhydrides ð47JOC0271Ł\ and N!phthaloylamino
pyrroles can be acylated with acid chlorides using zinc chloride as catalyst ð77JHC406Ł[
OBn OBn
O
POCl3
+ N Ph (112)
N 71% N
H H
O O
O
N HCl, H2O Cl
+ Cl CN (113)
N
NO2 53%
NO2
Electrophilic acylations of the FriedelÐCrafts type occurs preferentially at the 1!position "Equa!
tions "000# to "002##\ but the substitution pattern of the particular pyrrole substrate can markedly
e}ect this aspect of the reaction[ If the 1! and the 4!position are blocked\ acylations occur at the
2!position "Equation "003## ð79SC662Ł\ and a similar e}ect is noted if only the 1!position bears an
electron!releasing group or if the pyrrole nitrogen is protected with a bulky group ð74S242Ł[ Examples
of the latter include t!butyldimethylsilyl ð74TL4924Ł\ triisopropylsilyl "Equation "004## ð72TL2344Ł\
trityl ð72JCS"P0#82Ł\ t!butyl and adamantyl ð79JCR"S#31Ł[ Furthermore\ deactivating N!sulfonyl pro!
tection also promotes acylation at the 2!position "Equation "005## ð70TL3788\ 70TL3890\ 72JOC2103Ł^
electron!withdrawing groups at the 1!position direct acylation to the 3!position ð68TL1494\ 79CJC1416\
77H"16#0744Ł^ and in a somewhat surprisingly general manner 1!keto pyrroles can be isomerised to
the corresponding 2!keto derivatives on exposure to acidic conditions ð70JOC728\ 71JOC2557Ł[ Delivery
of acylating species by tethering to the nitrogen atom can provide 1!keto pyrroles selectively\
although mechanistic details are uncertain ð89TL884Ł[
But
N HI
+ (ButCO)2O N (114)
71%
OMe
OMe
O
O OEt
pyridine, CH2Cl2
+ OEt (115)
N Cl
70% O
tips O N
tips
tips = 1,1,3,3-tetraisopropyldisiloxane
297 Ketones With an a\b!Aryl or !Hetaryl
O
O
AlCl3
N + (116)
O S O Cl 99% N
Ph O S O
Ph
Pyrroles can be acylated in their C!1 positions using acid chlorides and bases such as sodium
hydroxide ð53AJC0945Ł\ triethylamine ð69LA"622#16Ł and 1\5!lutidine ð61JOC2507Ł[ However\ yields
are not usually good under such conditions\ and acylation reactions of lithio! and magnesiopyrroles
is far more e}ective[ N!Substituted pyrroles are readily lithiated at the 1!position on exposure to
alkyllithiums\ and the lithium species can then be successfully acylated with nitriles ð71SC120Ł\
benzamides ð80S0968Ł and lactones "Equation "006## ð70JOC2659\ 72CC529\ 73JOC2492Ł to provide the
corresponding ketones with complete regiocontrol[ Treatment of pyrroles with simple Grignard
reagents "e[g[\ MeMgBr# or transmetallation reactions of lithiated derivatives ð70JOC2659Ł provide
the corresponding magnesiopyrroles that will then react with acid chlorides ð54JHC362Ł to give
ketones in low yields\ or with low regiocontrol\ but are best acylated with pyridyl thioesters to
give high product yields "Equation "007## ð70TL3536Ł[ This latter approach is e}ective under mild
conditions and has been used in the preparation of a number of functionally complex compounds
"Equation "008## ð70JA5858\ 75T5354\ 76JA6442Ł[ Additions of metallated pyrroles to aldehydes and
subsequent oxidation\ usually with manganese dioxide ð72OS"51#000Ł\ of the resulting alcohols have
been used to prepare some ketones\ and the use of pyrrolic carboxylic acid derivatives as acylating
species for organometallic or aromatic substrates has also found utility in the preparation of pyrrolic
ketones "Equation "019# ð55T"S#130\ 70H"05#288\ 76AP"219#0919Ł[
O
O O
N
DME, 0 °C SEM
N Li + (117)
62% HO
SEM
SEM = β-trimethylsilylethoxymethyl
O toluene, –78 °C R
N + N (118)
R S N 90–95% H
MgCl O
O SPy
H
toluene, THF, –20 °C
+ O
N H H
MeO2C 90%
MgCl
H
O
N
H H
(119)
O
H H
MeO2C
H
O
O O
O O
EtO OEt
NaH EtO
OEt (120)
N 66%
N N
N
Me O
O OEt Me OEt
O
Hetaryl Ketones 298
2[95[3[5 Ketoindoles
Indoles are considerably nucleophilic and sometimes undergo uncatalysed FriedelÐCrafts acyl!
ation reactions with acid chlorides and anhydrides\ particularly on heating with the more reactive
of such compounds ðB!53MI 295!90Ł[ However\ most examples require a Lewis acid catalyst of which
zinc chloride ð61S422Ł\ and especially aluminum trichloride ðB!53MI 295!90Ł\ are the most popular
and e}ective[ Acylations with carboxylic acids and protic acid catalysts "Equation "010## ð58JA1231\
79H"03#0828Ł or with selenoesters and copper catalysts "Equation "011## ð79JA759\ 74T3710Ł have also
proved relatively useful\ as has the two!step method utilising 1!substituted!0\2!benzoxathiolium
ions ð76S200Ł[ In contrast to the analogous reactions of pyrroles\ electrophilic acylations of this type
generally occur at the 2!position[ However\ when blocked\ acylation at the 1!position occurs with
equal facility[ FriedelÐCrafts acylations can occur selectively at the 1!position when the 2!position
is unsubstituted by ipso!substitution of a trimethylsilyl group "Equation "012## ð78JOC3249Ł[ This
type of reaction has also been used in acylations of the 3!position ð73JOC3398Ł[ Competitive acylation
at the 2!position is avoided by acetylation of nitrogen and concomitant deactivation of the hetero!
cyclic ring "Equation "013##[ The 3!position can also be acylated electrophilically in indoles bearing
an activating group "e[g[\ OMe# at the 4! or 6!position\ and usually also with an electron!withdrawing
group on either the nitrogen atom or the 1!position ð30LA"438#127\ 66CPB2912\ 73JOC2084Ł[ FriedelÐ
Crafts acylations of simple indoles are not common at the 4! and 6!positions\ but they can occur
with varying selectivity when electron!withdrawing groups are present at the 1!position ð77CPB1912\
89CPB2150Ł[ 5!Acylations can occur in useful yields in the case of N!acetyl indoles ð30LA"438#127\
73JOC3398Ł[
O O
N
O H3PO4
N
(121)
OH 85%
N N
H H O
O CuOTf, benzene
N
+ (122)
MeSe 85%
Me N
Me
TMS
AlCl3, CH2Cl2
N + (MeCO)2O N O (123)
O 86% O
O S O S
Ph Ph
TMS O Cl
Cl O AlCl3
+ (124)
N Cl 75% N
O O
0!Indolylmagnesium halides are acylated preferentially at the 2!position "e[g[\ ð38RTC4\ 76TL2630Ł#
but often only in moderate yields[ 0!Methylindoles ð79JA0346Ł and 0!phenylsulfonylindoles
ð62JOC2213\ 70JOC1868\ 78JOC2153Ł are selectively lithiated in the 1!position using strong bases\ and
can subsequently be acylated e.ciently using acid chlorides or anhydrides[ In a related manner
0!"N!aroylcarbamoyl# indoles\ prepared from 0!"1!oxazolinyl#indole\ give 1!aroyl!0H!indoles\ on
treatment with lithium diisopropylamide "LDA#\ by an intramolecular acyl transfer "Equation "014##
ð82H"24#462Ł[ Additions of aldehydes to metallated indoles\ and oxidation of the resulting alcohols\
usually with manganese dioxide ð64JOC1502\ 73T2228\ 75T1200\ 89SC2958\ 82T1774Ł\ provide the desired
ketones\ and direct oxidation of an a!methylene in substituted indoles can lead directly to ketones
209 Ketones With an a\b!Aryl or !Hetaryl
using oxidants such as selenium dioxide "Equation "015## ð80CC0576Ł\ hydroiodic acid ð55JA0938Ł\
ddq ð65H"3#0748\ 78JOC1069\ 89T5512Ł and iodine pentoxide "Equation "016## ð70JA5889\ 76CPB3699Ł[
Ph
N i, PhCOCl, 95%
(125)
N ii, LDA, 73% N O
O H
O O
H OBn SeO2, dioxane H OBn
N (126)
N 43%
N H N H
H H O
Cl Cl
O O
I2O5, THF (aq.)
N (127)
N 65%
N N
H H
O
O
O
OH ppa
F (128)
N 85%
N
F
Direct lithiations of pyridines can be problematic due to the ready addition of alkyllithiums to
the pyridine ring system[ However\ transmetallations of pyridyl bromides are readily achieved at
low temperature\ and the resulting organometallic species can be acylated successfully[ Lithiated
pyridines prepared in this way are acylated in moderate yields with tertiary amides "Equation "018##
ð80JOC0711\ 81JOC650Ł\ nitriles ð48JA0827Ł and carboxylic acids ð82SC874Ł[ Grignard reagents show
similar utility "e[g[ ð82TL2572Ł#\ and they can also be prepared by the reaction of phenyl magnesium
bromide with pyridyl sulfoxides ð75TL2788Ł[ Pyridine N!oxides and some of their derivatives can be
deprotonated at the 1!position and subsequently acylated ð61JOC2473\ 75CB168\ 89H"20#316Ł[ Direct
lithiation of pyridines is possible with ortho!directing groups such as acylamino ð76CJC0047Ł\ chloro
ð70JOM"105#028\ 75S775Ł and amido groups "Equation "029## ð79JA0346\ 76T4170Ł[ Directing groups in
the 2!position usually stabilise 3!lithio derivatives\ but in some cases the 1!position can be lithiated
selectively ð70JOM"105#028Ł[
Hetaryl Ketones 200
O O
Cl Br ButLi Cl
NMe2 (129)
57%
N N
OMe O O NPri2
Li O OMe O
MeO
NMe2 MeO
+ NPri2 (130)
58%
N
N
OMe
OMe
1! and 3!Trimethylstannyl pyridines are acylated in variable yields on direct reaction with acid
chlorides ð71CPB1992\ 71H"08#30\ 74JOC4325Ł[ The 2!stannyl compounds require a palladium catalyst
for reaction to occur "Equation "020## ð81TL2992Ł\ as do similar reactions between pyridyl zinc
compounds and anhydrides ð81TL4262Ł[ Palladium catalysts are also e}ective in promoting imino
carbonylative cross!coupling reactions between bromopyridine and 8!alkyl!8!BBN derivatives
ð81TL3354Ł\ and between iodopyridine and boronic acids ð82TL6484Ł[ Under somewhat harsher
conditions\ a ruthenium catalyst has been shown to promote carbonylative coupling between
pyridine and alkenes ð81JA4777Ł[ Nucleophilic acyl radicals can add at the 1!position of pyridine to
give ketones in good to excellent yield "Equation "021## ð63JCS"P1#0588\ 78H"17#378\ 80JOC1755Ł\ and
cyanohydrins derived from pyridyl aldehydes are readily lithiated\ alkylated and _nally hydrolysed
to provide the desired ketones ð68CB1934\ 73SC632Ł[ Oxidations of alcohols to pyridyl ketones are
best achieved with relatively mild oxidants such as manganese dioxide ð71JA425Ł and DessÐMartin
periodinane ð82TL220Ł[
OBn OBn
SnMe3 O O
O N PdCl2(PPh3)2 O N
+ O (131)
O 48%
N Cl
O O
N
O
O
O O
S
S OMe
O O
Li + (134)
N 80% N N
N O O
ButO ButO
i, BuLi
N Cl
ii, N
N TBDMS O
TBDMS (135)
O S O N
91%
OO S O
NMe2
NMe2
Cl
N Cl O N
tbaf, THF, benzene
TMS + (136)
O O O 60%
S HO S
O
tbaf = tetra-n-butylammonium fluoride
Copyright # 1995, Elsevier Ltd. All R ights Reserved Comprehensive Organic Functional Group Transformations
3.07
Aldehyde and Ketone Functions
Further Substituted on Oxygen
DONALD A. WHITING
University of Nottingham, UK
2[96[0 CARBONYL YLIDES 202
2[96[0[0 Introduction 202
2[96[0[1 Carbonyl Ylides From Oxiranes 204
2[96[0[1[0 Intramolecular cycloadditions^ oxirane to oxy`en heterocycle 204
2[96[0[1[1 Intermolecular cycloadditions^ oxirane to oxy`en heterocycle 206
2[96[0[1[2 Electrocyclizations leadin` to furans and oxepines 207
2[96[0[1[3 Trappin` by hydroxyl functions leadin` to acetals 208
2[96[0[1[4 Trappin` by oxy`en leadin` to ozonides 208
2[96[0[2 Carbonyl Ylides From Carbenes 208
2[96[0[2[0 Intramolecular cycloadditions^ diazocarbonyl to oxy`en heterocycle 208
2[96[0[2[1 Intermolecular cycloadditions^ carbene to oxy`en heterocycle 219
2[96[0[2[2 Electrocyclizations leadin` to furans 210
2[96[0[2[3 Hydro`en mi`ration leadin` to enol ethers 212
2[96[0[2[4 Halo`en mi`ration and decarbonylation reactions 212
2[96[0[3 Carbonyl Ylides From Cycloreversions 212
2[96[0[4 Carbonyl Ylides From Elimination Reactions 213
2[96[0[0 Introduction
Carbonyl ylides are 0\2!dipolar species\ represented by the parent 1!oxatrimethylene structure
"0#[ This ylide is conveniently shown in the zwitterionic form\ although calculations show signi_cant
diradical character ð68JA0984\ 68JA0090\ 79JA0493Ł and indicate a preferred nonlinear\ planar geometry
"the 9>\ 9> conformation#[ Theoretical studies also suggest that the stability of such ylides would be
increased by substitution by electron!donating groups at one carbon centre and electron!with!
drawing groups at the other\ when dipolar zwitterionic character is enhanced and the energy barriers
to rotation are lowered[ In an extreme case "1#\ the "9>\ 89># conformation should be favoured[
+
+ H2N O – CN
H O H
–
CN
H2N
H H
(1) (2)
202
203 Further Substituted on Oxy`en
Carbonyl ylides are generally encountered as reactive intermediates rather than stable species^
they have been observed spectroscopically "at low temperatures and trapped in matrices# in several
cases[ Thus irradiation of tetraphenyloxetanone "2# at wavelengths ×166 nm leads to expulsion of
carbon monoxide and production of the blue ylide "3#\ identical to that obtained by irradiation of
tetraphenyloxirane "4# "Scheme 0# ð69JA0391Ł[ Both thermolysis and photolysis of the 4!oxabicyclo!
ð1[0[9Łpentane "5# have yielded the colored\ _ve!membered ring ylide "6# "Equation "0##[ In the case
of the ylide "6#\ when RPh\ the species displayed a t0:1 of 7 min[ This relatively long lifetime is
ascribed to the unfeasibility of thermal ring closure to the highly strained trans!fused bicycle\
through the allowed conrotatory process ð69JA0393\ 69PAC412\ 60JHC0986Ł[ A study of the reaction
with acetone of the carbene "7#\ generated by laser photolysis of diazo~uorene\ showed the formation
of the ylide "8# "Scheme 1#[ The decay of the intermediate "8# was interpreted as requiring rotation
from the initial 9>\ 9> conformation to the 9>\ 89> geometry before collapse to the oxirane "09#
"Scheme 1# ð74JA6193Ł[ One example is known of a stable carbonyl ylide\ this is "00#\ which exists
as a crystalline solid in the 9>\ 89> shape[ The stability of "00# arises from the extreme {push!pull|
electronic e}ects ð72JA4818Ł[ One metal complex "01# of a carbonyl ylide has also been reported
ð61JOM"35#C18Ł[
Ph O Ph + O
hν, > 277 nm Ph O Ph 254 nm Ph Ph
Ph Ph –
77 K 77 K Ph Ph
O Ph Ph
(3) (4) (5)
Scheme 1
O +
Ph R Ph O – R
∆ or hν
(1)
(6) (7)
:
+O O
Me2CO –
Scheme 2
+
CF3
Me2N O – O
NC CN
CF3
Me2N NC Pt CN
F3C
CF3 Ph3P PPh3
(11) (12)
This review concentrates on synthetic aspects of the carbonyl ylide area[ Historical\ theoretical\
and mechanistic aspects are outside the scope of this chapter\ and the reader is referred to major
general reviews of the _eld\ inter alia ðB!73MI 296!90\ 80COS"3#0978\ 80COS"3#0048Ł[ Carbonyl ylides are
formed by four general processes] "i# thermal or photochemical carbon0carbon bond cleavage in
epoxides^ "ii# carbene additions to carbonyl groups^ "iii# cycloreversion reactions^ and "iv# elimination
processes[ The _rst three of these processes are exempli_ed in the formation of the ylides "3#\ "6#\
and "8#[ The various subsections of this review will treat each mode of ylide formation in turn\
illustrating the transformations observed with examples chosen to highlight the range of reactions
of these reactive novel intermediates[
Carbonyl Ylides 204
2[96[0[1 Carbonyl Ylides From Oxiranes
Carbon0carbon bond cleavage of oxiranes\ induced thermally\ photochemically\ or by electron
transfer catalysis\ is a common method of generating carbonyl ylides[ Either conrotatory or dis!
rotatory ring openings are possible^ these are formally allowed either thermally "conrotatory# or
photochemically "disrotatory#^ exo!exo or exo!endo ylide conformations result "Scheme 2#[ In prac!
tice\ situations are complicated by the thermal interconversion of the two conformations\ and by
violation of orbital symmetry control in the face of acute steric constraints ð60CC0089\ 60CC0081\
65TL3532\ 66CC328\ 66CC339Ł[ The overall outcome is dependent on the relative kinetics of ring opening\
conformational equilibration\ and the rate of trapping by a dipolarophile[ As a consequence\ varying
degrees of stereospeci_city have been observed[ The cycloaddition reactions of carbonyl ylides are
usually regioselective\ and the regiochemistry can be rationalized by Frontier Molecular Orbital
"FMO# theory\ with the HOMO of the dipole dominant for reactions with electron!de_cient species\
while the LUMO becomes important for addition to electron!rich alkenes[
O ∆, conrotatory +
R H R O R
–
H R exo-exo
hν, disrotatory
+
O ∆, conrotatory R O
R R –
H H R
exo-endo
Scheme 3
Ph O Ph Ph Ph O Ph
O 450 °C, 10 s
hν, disrotatory conrotatory
Ph
35% 25%
CO2Me H CO2Me CO2Me
(13) (14) (15)
Scheme 4
205 Further Substituted on Oxy`en
O
Ph Ph
H
R = H, 175 °C, 9 h CN
CN (2)
n = 1, 75% (40% conversion)
n = 1, 66% (30% conversion) ( )n H
n( )
R
(16) (17)
O Ph
CN
O
MeO2C
(18)
O
Ph
CN 180 °C, 6 h O
O H CN (3)
90% O
Ph
H H
(19) (20)
Ph MeO2C
O NC
245 °C, 22 h NC 3 O
10( ) 4
(4)
O 42% Ph O O
MeO2C
(21) (22)
MeO2C
O
CO2Me CO2Me
O
160 °C, 13 h
CO2Me (5)
76%
O
O
(23) (24)
O O
300 nm, PhH
(6)
65% O
O
(25) (26)
O O
(27) (28)
Carbonyl Ylides 206
2[96[0[1[1 Intermolecular cycloadditions^ oxirane to oxygen heterocycle
An early example of these cycloadditions is a}orded by the thermal C0C bond scission of
tetracyanoethylene oxide "18#^ the resulting ylide was particularly reactive\ not only yielding an
adduct "29# "49)# with styrene\ but also a product "20# "32)# with p!xylene ð54JA2546Ł[ A cyclic
ylide is formed on photolysis or pyrolysis of the indenone oxide "21#\ which can be trapped with\
for example dimethyl acetylenedicarboxylate "DMAD#\ bicycloð1[1[0Łheptadiene\ or cyclohexanone
to provide the varied products "22#\ "23#\ and "24# respectively "Scheme 4# ð51JA0204\ 53JA2703\
53TL0736\ 60CJC2332Ł[
CN
NC CN H CN
O O
NC CN
NC CN O
NC CN
Ph H CN
CN
(29) (30) (31)
CO2Me
O Ph
R hν, PhH
O CO2Me
O 40%
Ph R
O
(32) (33)
145 °C, 16 h
hν, 63% 83%
O Ph
O
O
Ph Ph
O
O
(34) (35)
Scheme 5
Electron transfer photosensitization o}ers an alternative mode of generating carbonyl ylides from
epoxides[ A sensitizer\ for example dicyanonaphthalene or dicyanoanthracene\ in a photochemically
excited state extracts an electron from the oxide\ which then ring opens to the corresponding cation
radical equivalent of the ylide before reclaiming an electron ð67CJC1874Ł[ The isomerization of cis!
to trans!stilbene oxide\ "25#:"26# "Equation "7##\ can be observed under these conditions\ and
the intermediate can be trapped with fumaronitrile and maleonitrile to yield the corresponding
tetrahydrofurans "27# "76)# and "28# "42)# with other minor stereoisomers in each case ð67CJC1874Ł[
Interception with maleic anhydride\ and the less reactive 1!butenolide\ has a}orded the bicyclic
ethers "39# "52)# and "30# "32)# respectively ð89JCS"P0#042Ł[ Attempts to generate a carbonyl ylide
from bis"3!methoxyphenyl#oxirane "31^ Ar3!methoxyphenyl# thermally or by direct or triplet
sensitized irradiation were frustrated by preferential C0O bond cleavage\ leading to deoxyanisoin
and bis"3!methoxyphenyl#ethanal[ However electron transfer sensitization "ET sens# using dicyano!
naphthalene\ and through phenanthrene!toluene _lters\ allowed formation of the desired ylide\
trapped by DMAD to a}ord "32# "43)# ð89JCS"P0#042Ł[
O hν, ET sens O
(8)
Ph Ph Ph Ph
(36) (37)
Ph O Ph Ph O Ph
(38) (39)
Ph O Ph Ph O Ph
Ar O Ar
O
H H H H
Ar Ar
O O O MeO2C CO2Me
O O
(40) (41) (42) (43)
Ar = 4-methoxyphenyl
rise to products "34# and "35# in nearly equal proportions "Equation "8## ð76TL2044\ 89JCS"P0#0082Ł[
Related cases were observed\ and the ylide intermediates may have high radical character[
Ar1 Ar1
O NO2 O Ar2 O Ar2
110 °C
NC + NC (9)
Ar 75%
CN MeO2C CO2Me
(44) (45) (46)
Ar1 = 4-nitrophenyl; Ar2 = 3,4-methylenedioxyphenyl
NC NC Ph
O 325 °C
O (10)
Ph 65%
O CO2Me O
MeO2C CO2Me
CO2Me 390 °C
O
50%
MeO2C CO2Me
(49) (50) (51)
Scheme 6
Carbonyl Ylides 208
R2 R1 R2
R1 SMe SMe (11)
O SMe O SMe
(52) (53)
O
Ph Ph
200 °C, 1 h O
+ (12)
O Ph
CO2Me CO2Me
MeO2C
(54) (55) 22% (56) 53%
cis : trans = 4 : 3
(57) (58)
O
O
O hν, MeOH O [3,3]
O
O 43%
OMe
OMe
(59) (60) (61)
Scheme 7
In the 0879s the formation of carbenes from diazocarbonyl compounds catalyzed by rhodium"II#
salts\ especially rhodium acetate\ has attracted much attention[ This method allows mild conditions\
reactions often taking place at ambient temperature in a few hours[ Thus the diazoketone "53# with
rhodium acetate loses nitrogen to form the corresponding ketocarbene^ the carbene then is trapped
by the adjacent ester carbonyl functionality to give an ylide which _nally undergoes intramolecular
cycloaddition to form the tricyclic furanone "54# "Scheme 7# ð71T0366Ł[ The phthalate derivative
"55# under similar circumstances yields the bridged furofuran "56# "Equation "05##^ the intermediate
in this reaction can also be intercepted with DMAD ð77JA1783Ł[ The acyclic functional assemblies
"57# and "69# undergo related reaction cascades to provide the tricyclic heterocycles "58# and "60#
respectively "Equations "06# and "07##^ in the _rst case an isomunchone!like ylide intermediate
participates ð77TL0566\ 78JOC706Ł^ cf[ ð82TL6742Ł[
O O
COCHN2 Rh2(OAc)4, 3 h, RT
–
CO2Et 43% EtO2C
EtO O+ O
(64) (65)
Scheme 8
N2 O
Rh2(OAc)4, 25 °C
O O (16)
O 87%
O O
(66) (67)
O
O O O
Rh2(OAc)4, 110 °C O
( )3 N (17)
91% N O
N2
Ph
Ph
(68) (69)
O
Rh2(OAc)4
( )3 N2 O (18)
O
O
(70) (71)
O CO2Me
CO2Me Ph O Ph
∆, cat. CO2Me
PhCHO + N2 + CO2Me (19)
CO2Me O
CO2Me
Ph
(72) (73)
Cl O
Ar O Ar Cl
DMAD
ArCHO + PhHgCBrCl2 Cl + (20)
PhH, 80 °C
MeO2C CO2Me MeO2C CO2Me
(74) (75)
Two examples of intermolecular reactions of ylides from diazocarbonyl reactants are provided
by the work of Padwa and co!workers ð78CC810\ 78TL0380\ 89JA2099\ 82JOC3535Ł[ Thus\ the diazoester
"65# with N!phenylmaleimide gave the bridged furolactone "66# "Equation "10##\ while the diazo!
ketone "67# reacted with propanal to yield bridged cyclic acetals "68^ XO# and "79^ XO#
"59)\ 1 ] 0#\ which were deoxygenated to exo! and endo!brevicomin "68^ XH1# and "79^ XH1#
respectively "Equation "11##[ The last case in this subsection illustrates the scope for intramolecular
reactions of carbenes with amide carbonyl groups "70# to form ylides "71#\ which can equilibrate
with their isomers "72# through hydrogen transfer^ both of the ylides can be trapped by DMAD
"Scheme 8# ð81JA482Ł[
Ph
O N2 O N O
Rh2+, 80 °C, N-Phenylmaleimide
O
R Z (21)
75–85% R Z
O
O
(76) O O
Z = CO2Et, CN; R = Me, Ph
(77)
O
N2 Rh2+, EtCHO O O
O + O H (22)
O Et
X X Et
(78) (79) (80)
O – O
O Rh2+
N N N
–
R O N2 R O+ R O+
Scheme 9
CO2Me
CO2Me
(84) (85)
NPri2 NPri2
NPri2 CO2Me
O Cu(acac)2 dimethyl maleate
O 75%
CO2Me
N2 OH
(86) (87) (88)
Scheme 10
O O
O O
O O
Cu (F6 - acac)2
(24)
O
O H
N2
MeO MeO
CO2Me CO2Me
(89) (90)
Further variants are o}ered by the cyclization of vinyl carbenes to fused furans[ The diazoketone
"80# with an alkyne side chain is converted by rhodium acetate into the corresponding ketocarbene\
which cyclizes _rst to the vinyl carbene "81#\ then to the furan "82# through a formal 0\2!dipole
"Scheme 00# ð89JOC303Ł[ Parallel chemistry is displayed in the formation of the furolactone "84#
from the acyclic diazoester "83# "Equation "14## ð89TL5724\ 82JOC10Ł[
O O
:
O
Rh2(OAc)4
N2
85%
Scheme 11
R
R O
O O Rh2(OAc)4, 80 °C
(25)
O O
O
N2
(94) (95)
Carbonyl Ylides 212
2[96[0[2[3 Hydrogen migration leading to enol ethers
Carbonyl ylides with suitably disposed hydrogen atoms can rearrange by hydrogen migration to
the anionic site\ as illustrated in Scheme 01[ The enol ether "83# is the major product although a
little ylide is trapped by cyclohexanone to form the dioxolane "84# ð42JOC0929\ 78TL3978Ł[ With
1!methylcyclohexanone\ regioselective enolization results ð67JOC0133Ł[ Another example arises in
the decomposition of the diazoketone "85# where 0\2!hydrogen shift in the ylide leads to the furan!
2!one "86# "Equation "15## ð80JOC2160Ł[
CO2Et CO2Et
N2 EtO2C
O CO2Et
+ –
Cu, 90 °C O O
+ O O
Scheme 12
O O
N2 Rh2+, 25 °C
(26)
90%
EtO O
EtO O
(96) (97)
+
80 °C Ar O – Cl
ArCHO + PhHgCBrCl2 CO + ArCHCl2
Cl
Scheme 13
O
N-phenylmaleimide, 60–65 °C Ph
O OAc (27)
51% O
N N Ph N O
Ph
(98) (99)
RO
O PhH, 100 °C MeO OR (30)
MeO
:
N N
(106) (107)
+
Ar N Me2CO, 80 °C Ar O
– (31)
Cl N
Cl
(108) (109)
Me O
Me O– MeO2C CO2Me
N
N DMAD
Ph Ar
O
Ph O Ar –MeNCO Ph Ar
+
O
MeO2C CO2Me
(110) (111) (112)
Scheme 14
Ph O Ph
+O Ph
O Ac2O, 80 °C CO2Me N
N
N CO2H –COS
S O–
S MeO2C
(113) (114) (115)
Scheme 15
O O O
dbn, RT O
–
AcO O O 75%
–AcOH +
H
(116) (117) (118)
Scheme 16
O
O
O O
AcO O
EtO O
(119) (120) (121)
O O
O
H H
Et3N, RT
O + O (32)
O cyclohexenone
H H
OAc
O O
(122) (123) (124)
OAc
OAc
O
dbu, RT
O (33)
O
O-TBDMS
O-TBDMS O
OAc
(125) (126)
dbu = 1,5-diazabicyclo[5.4.0]undec-5-ene; TBDMS = t-butyldimethylsilyl
215 Further Substituted on Oxy`en
0\2!Elimination from chloromethyl!a!trimethylsilyl!a!arylmethyl ethers "016# has been shown to
lead to the formation of simple aryl carbonyl ylides "017# under mild neutral conditions following
chemistry parallel to that of the nitrogen analogues "Equation "23## ð82TL4832Ł[
Ar
Ar CsF, RT
– (34)
O
TMS O Cl
+
(127) (128)
Finally an isolatable 2!oxidopyrilium ylide has been obtained from the thiopyrilium perchlorate
"018#[ S!Phenylation of "018# followed by treatment with oxygen _rst gave the cyclic peroxide "029#
which next rearranged on reaction with hydrogen chloride with loss of thiophenol to form the ylide
"020# as a dark red solid "Scheme 06#^ the ylide "020# then gave an adduct with maleic anhydride
ð51JA1983Ł[
Ph Ph Ph
i, PhLi HCl, Et2O O–
O O
Ph S Ph ii, O2
+
Ph S Ph Ph O Ph
ClO4 – Ph +
Scheme 17
O3, –70 °C O O O O O O
+ + (35)
O O O
O D D3C D
O D D
D
D O3 O O
O D D + O (36)
D D O O
D
D
O
(135) (136) (137)
216
R1 OOH O O
R1
R2 O
R1 OMe R1
MeOH
R2CHO
O O–
O O + O O O
O R1 R1
+
R1 R1
R1 R1 R1 R1 R1 O R1
R1 R1
R1 O O R1
R1 O O R1
Scheme 18
O O O O
O3 +
O O
O–
O
(132) (133) (134)
Scheme 19
Sensitized photooxygenation of furans\ for example "027# has been shown to lead to a reaction
sequence involving a!unsaturated carbonyl oxides "028# as intermediates "Equation "26##[ The latter
display a range of reactions\ including cycloadditions ð83JCS"P0#036Ł[
CO2Me CO2Me
hν, O2
(37)
Ar CO2Me
Ar O OMe O O–
+
(138) (139)
Copyright # 1995, Elsevier Ltd. All R ights Reserved Comprehensive Organic Functional Group Transformations
3.08
Thioaldehydes and Thioketones
WILLIAM G. WHITTINGHAM
ZENECA Agrochemicals, Bracknell, UK
2[97[0 INTRODUCTION 229
2[97[1 THIOALDEHYDES 220
2[97[1[0 Alkyl Thioaldehydes 220
2[97[1[0[0 Photolysis of phenacyl sul_des 220
2[97[1[0[1 Formation of the a C0C bond 221
2[97[1[0[2 0\1!Elimination reactions 222
2[97[1[0[3 Cycloreversion and related reactions 223
2[97[1[0[4 Sulfuration of aldehydes and derivatives 225
2[97[1[0[5 Other methods 225
2[97[1[1 a\b!Unsaturated Thioaldehydes 226
2[97[1[1[0 Thioaldehydes bearin` an a\b!alkenic bond 226
2[97[1[1[1 Thioaldehydes bearin` an a\b!aryl or hetaryl substituent 239
2[97[1[1[2 Thioaldehydes bearin` an a\b!alkynic bond 231
2[97[2 THIOKETONES 231
2[97[2[0 Dialkyl Thioketones 231
2[97[2[0[0 Dialkyl thioketones by sulfuration of ketones 232
2[97[2[0[1 Dialkyl thioketones by direct sulfuration of other compounds 236
2[97[2[0[2 Dialkyl thioketones by other methods 238
2[97[2[1 a\b!Unsaturated Thioketones 241
2[97[2[1[0 Thioketones bearin` an a\b!alkenic bond 241
2[97[2[1[1 Thioketones bearin` an a\b!aryl or hetaryl substituent 259
2[97[2[1[2 Thioketones Bearin` an a\b!Alkynic Bond 255
2[97[3 THIOALDEHYDE AND THIOKETONE FUNCTIONS FURTHER SUBSTITUTED
ON SULFUR 255
2[97[3[0 Two!coordinate Sulfur Functions 256
2[97[3[0[0 Thiocarbonyl ylides 256
2[97[3[0[1 Sul_nes 257
2[97[3[0[2 Thiosul_nes 269
2[97[3[0[3 Thiocarbonyl S!imides 269
2[97[3[0[4 Metal complexes of thioaldehydes and thioketones 269
2[97[3[0[5 Thiopyrylium salts 269
2[97[3[0[6 0\1!Dithiolium salts 260
2[97[3[0[7 Nonclassical thiophenes 260
2[97[3[0[8 Other heterocycles 261
2[97[3[1 Three!coordinate Sulfur Functions 261
2[97[3[1[0 Sulfonium ylides 261
2[97[3[1[1 Sulfenes 264
2[97[3[1[2 Other simple systems 264
2[97[3[1[3 Thiabenzenes 264
2[97[3[1[4 0\5\5al3!Trithiapentalenes and related systems 265
2[97[3[2 Four!coordinate Sulfur Functions 267
2[97[3[2[0 Sulfoxonium ylides 267
2[97[3[2[1 Other simple compounds 268
2[97[3[2[2 Thiabenzene S!oxides 268
2[97[3[3 Five!coordinate Sulfur Functions 279
2[97[3[3[0 Alkylidene sulfur tetra~uorides 279
218
229 Thioaldehydes and Thioketones
2[97[0 INTRODUCTION
Although the chemistry of the C1S double bond bears many similarities to that of the C1O
bond\ there are some signi_cant di}erences[ The C1S bond is much less polarized than the C1O
bond\ because of the much smaller di}erence between the electronegativities of carbon "1[49# and
sulfur "1[47# than between those of carbon and oxygen "2[33#[ Thus\ whereas the carbonyl bond has
a clear polarization\ with a partial negative charge on oxygen and a partial positive charge on
carbon\ the situation for the thiocarbonyl bond is much less clear cut[ The greater length of the
C1S bond also leads to a bond that is more easily polarized by neighboring groups[ This results in
large variations in the reactivity of di}erent thiocarbonyl groups^ an e}ect that is not seen for
carbonyl compounds[ For example\ electron!withdrawing groups on the thiocarbonyl carbon atom\
as in hexa~uorothioacetone\ signi_cantly reduce the electron density on sulfur\ and can reverse the
expected polarity of the C1S bond\ resulting in nucleophilic attack occuring at sulfur rather than
carbon ð54JOC0273Ł[ On the other hand\ conjugative electron!donating groups "as in\ for example\
thioesters and thioamides# result in the opposite sense of polarization and hence in compounds with
a strongly nucleophilic sulfur atom[
Thiocarbonyl compounds bearing electroneutral groups\ such as carbon and hydrogen\ tend to
have nonpolarized C1S bonds and can thus react in di}erent ways\ depending on the conditions[
This results in the very ready oligomerization or polymerization of thioaldehydes and thioketones\
and many of these compounds are highly unstable and can only be isolated under special conditions\
if at all[ For this reason many simple thioaldehydes and thioketones\ and their derivatives\ have
been generated and characterized only at very low temperatures\ or in the gas phase[ Although these
compounds are not strictly within the scope of this review\ their preparation will be detailed where
it demonstrates a useful principle\ or if the method could potentially be applied to the synthesis of
stable compounds[ The same criteria have been applied to those cases where the thiocarbonyl
compounds have been generated and then trapped in situ without isolation or characterization[ This
approach has been widely used\ not only for the characterization of the thiocarbonyl compounds\
but also in a number of synthetic applications[
The C1S double bond is also signi_cantly weaker than the C1O bond "004 kcal mol−0 "370 kJ
mol−0# against 051 kcal mol−0 "567 kJ mol−0##[ This not only increases the reactivity of the
thiocarbonyl group\ it also radically changes the balance of the tautomerism between the thione
and enethiol forms of these compounds[ Thus the enethiol form is often the more stable and\ under
some circumstances\ can be formed exclusively in a reaction or by subsequent equilibration[ A
slightly di}erent manifestation of this e}ect occurs in the case of a!dithiones\ which can tautomerize
to 0\1!dithietes "Equation "0##[ In this case the position of the equilibrium is very dependent on the
further substitution of the system ð72HCA790Ł[ A similar acyclicÐcyclic tautomerism is possible for
a!ketothiones and a\b!unsaturated thiocarbonyls[ In these cases the equilibrium lies completely
toward the acyclic thione tautomer\ unless there is a very strong driving force for formation of the
C1C double bond as in\ for example\ monothio o!quinones "Equation "1## and o!thioquinone!
methides[ A more detailed analysis of the tautomerism of thiocarbonyl compounds is given by
Schaumann in his recent excellent review of the thiocarbonyl group ðB!78MI 297!90Ł and by Duus in
an earlier review ð68COC"2#262Ł[ For the purpose of this work\ brief mention will be made of synthetic
methods which result in the exclusive formation of enethiols or cyclic tautomers*further details
can be found in Chapter 1[03[0[
R S R
S
(1)
S
R S R
S
S
(2)
O
O
A further notable di}erence between thiocarbonyl and carbonyl compounds is a result of the
ability of the sulfur 2d orbitals to participate in bonding[ This\ combined with the lower elec!
tronegativity of sulfur than oxygen\ results in a rich chemistry of thiocarbonyl compounds that are
further substituted on sulfur which has no real equivalent in the chemistry of the carbonyl group[
A wide range of compounds of this type have been prepared\ and are discussed in Section 2[97[3[
Thioaldehydes 220
2[97[1 THIOALDEHYDES
As has been mentioned above\ the low polarization of the thioaldehyde bond means that many
of these compounds are unstable\ often forming cyclic dimers or trimers\ or polymers[ Indeed\ the
only thioaldehydes that can be isolated under normal conditions are those which have stabilizing
steric or electronic interactions[ This has resulted in the chemistry of thioaldehydes being much less
well developed than that of thioketones\ in which there are two potentially stabilizing groups[ The
_rst stable thioaldehyde was only prepared in 0859\ by Woodward et al[ as an intermediate in their
synthesis of chlorophyll a ð59JA2799Ł[
Signi_cant advances have followed\ notably in the use of reactive thioaldehydes in total synthesis
by the in situ trapping of these compounds as they are generated[ In particular\ thioaldehydes react
readily as dienophiles in the DielsÐAlder reaction\ a technique that has been developed extensively
by the groups of Baldwin\ Kirby\ and Vedejs[ The use of this method\ and of thiocarbonyl chemistry
in general\ for the formation of carbonÐcarbon bonds has recently been reviewed ð81S0074Ł[ A
number of stable thioaldehydes have been prepared and isolated\ generally in those cases where
electronic factors allow conjugation and delocalization of the thiocarbonyl bond\ or where extreme
steric crowding disfavors polymerization[
S R1 S R1 S R1
hν R2O
Ph O Ph OH R2O
Scheme 1
H
hν
71%
S S S
H
Ph
O
Scheme 2
Vedejs and co!workers have used this technique to prepare thiopivaldehyde "0#\ the _rst example
of a stable simple alkyl thioaldehyde ð72JA0572\ 75JA1874Ł[ Photolytic cleavage of phenacyl neopentyl
sul_de "1# provided the white insoluble thiopivaldehyde polymer[ The yield of this fragmentation
could be improved to 49Ð59) under optimum conditions "photolysis in benzene solution containing
an excess of 1\2!dimethylbutadiene\ using light _ltered through aqueous copper sulfate to remove
short!wavelength radiation that decomposes the polymer#[ Cracking the polymer at 149>C\ and
collection of the volatiles in a liquid nitrogen trap\ provided monomeric thiopivaldehyde "0# as a
magenta solid "Scheme 2#[ Addition of an inert solvent and warming to room temperature resulted
in a pink solution that was stable for up to 05 h\ depending on the cleanliness of the glassware and
221 Thioaldehydes and Thioketones
the purity of the solvents used[ Impurities\ especially protic or Lewis acids\ resulted in a more rapid
decomposition to the polymer and trimer[ The thiopivaldehyde was not particularly air!sensitive\
and underwent many reactions typical of thioaldehydes[ Other tertiary thioaldehydes can also be
prepared as monomers by this method ð75JA1874Ł[
S But
hν ∆
(ButCHS)n S But
59%
Ph O
(2) (1)
Scheme 3
(4) (3)
Scheme 4
Vedejs et al[ have prepared thiopivaldehyde by an alternative route to the photolytic method
described above\ which is conceptually similar to that used for the synthesis of the phosphonium
ylide!stabilized thioaldehydes "Scheme 4# ð75JA1874Ł[ Addition of t!butyllithium to ethyl thiono!
formate provided the hemithioacetal "4#\ which underwent acid!catalyzed decomposition to thio!
pivaldehyde\ which was distilled and trapped as before[ A similar technique has been applied to
the preparation of the highly sterically hindered thioaldehyde "5# by Okazaki et al[ "Equation "2##
ð76JA168Ł[ In this case\ reaction of the alkyllithium with ethyl thionoformate gave a 05) yield of
the thioaldehyde "5#\ a stable crystalline compound which could be puri_ed by chromatography
and recrystallization[ A further product "6# was isolated in 14) yield and is believed to derive from
the hemithioacetal "7#\ suggesting that an improvement in the yield of the thioaldehyde is possible
if "7# could be decomposed following Vedejs| method[
S ButLi SH H+, ∆ S
Scheme 5
TMS
S TMS Li
S
TMS TMS
OEt (3)
16% TMS
TMS
(6)
SH
TMS TMS
OEt OEt
TMS
TMS TMS
(7) (8)
Thioaldehydes 222
A related method has been used by Hartke and Gunther to prepare thioformyl acetonitrile
ð62LA0526Ł[ This compound could not be isolated\ but was moderately stable in solution\ existing
exclusively as the enethiol tautomer[
H
X R S
+ HX (4)
R S
O
Et3N
S N EtO2C S (5)
EtO2C 78%
O (9)
A further development of this general method has been reported by Kra}t and Meinke\ who have
used the ~uoride!induced cleavage of a!silyl disul_des "00# to generate a range of alkyl thioaldehydes\
which have been trapped by reaction with cyclopentadiene\ in good yields "Equation "7## ð74TL0836Ł[
A related approach has been described by Vedejs et al[ "Equation "8## ð77JA4341Ł\ although this
method has not been applied widely[ These two modi_cations of the 0\1!elimination technique have
the advantage that a wider range of thioaldehydes can be prepared\ as no adjacent activating group
is required[
CsF or tbaf
R2Me2Si S R1 S (8)
S 58–94%
X
R1
(11)
SO2Ph Et2NH
R S (9)
R SAc 29–77%
A related elimination strategy has been devised which relies on elimination from "or cycloreversion
of# a suitably activated dithiolane or derivative[ Thus\ deprotonation of the sulfonium salt "01#
forms an ylide which fragments to generate a thioaldehyde "Scheme 5# ð74TL4154Ł[ This method has
been used to prepare thioformaldehyde and thioacetaldehyde\ both of which were trapped in situ[
223 Thioaldehydes and Thioketones
Thiopivaldehyde was also prepared as a polymer\ which could be thermally cracked to the monomer
as described above[ A recent modi_cation of this method has also been used to synthesize thio!
pivaldehyde "Equation "09## ð89JOC3199Ł[ A variation of the procedure\ the thermolysis of a 0\0!
dioxodithiolane\ has been used to generate tri~uorothioacetaldehyde\ which was characterized in
an argon matrix and trapped as DielsÐAlder adducts ð78TL3000\ 89CB066Ł[ This thioaldehyde proved
to be rather unstable\ forming a polymer in a few minutes at −085>C[
S CO2Me CO2Me
EtNPri2 S
R R R S
+ + – 24–65%
S CO2Me S CO2Me
(12)
Scheme 6
O
TBDMS-OTf, EtNPri2
S But S (10)
But 39%
S
TBDMS = t-butyldimethylsilyl
Vedejs et al[ have demonstrated that cyanothioformaldehyde can be prepared by the reaction of
dibromoacetonitrile with EtOCS1−K¦\ a reaction that is mechanistically similar to other 0\1!
elimination approaches ð79JOC1590Ł[ The thioaldehyde could be trapped by dienes in low yield
"Scheme 6#[ This method could potentially be extended to the synthesis of other thioaldehydes\ but
appears to have been superseded by the Norrish type II photofragmentation technique[
S S CN
Br2HCCN EtO
S CN
K+ –S OEt 15%
EtO
Scheme 7
O
∆ S
S S
S 74%
Scheme 8
∆
HCHS + H2C CH2 (11)
S
S S
hν
O (12)
O O
(13) (14)
The most widely used method of this type involves the retro DielsÐAlder reaction[ As has been
discussed above\ the trapping of reactive thioaldehydes with dienes\ most commonly cyclo!
pentadiene\ is the method of choice for the isolation and characterization of these unstable
compounds[ Heating the DielsÐAlder adducts regenerates the free thioaldehydes\ which can be
trapped ð72CC0214Ł or\ in the case of thiopivaldehyde\ isolated in a liquid nitrogen trap "Equation
"02## ð77JA4341Ł[ A wide range of thioaldehydes can be generated in this way\ and conventional
chemistry can be used to elaborate the starting DielsÐAlder adducts and hence the _nal thioaldehydes
"Scheme 8# ð77JOC1119Ł[ A variety of di}erent adducts can be used to prepare thioaldehydes in good
yield ð72CC312\ 72T0376\ 74JCS"P0#0430\ 89JOC1485Ł[ A particularly useful variant of this reaction has
been reported by Lee et al[ "Scheme 09# ð74JOC2105Ł[ In this case the precursor "04# is prepared by
a di}erent route\ potentially allowing the synthesis of thioaldehydes not available by other methods[
S ∆
But S (13)
75%
But
O
O O
i, NaH, MeI S
ii, NaH, ClCH2C(Me)CH2, NaI ∆ EtO2C
CO2Et
S 35% S
CO2Et
Scheme 9
EtO2C
Cl3C SCl2 S CCl3 ∆
CO2Et EtO2C S
HN N
NH2 33% 85%
O
CCl3
(15)
Scheme 10
The retro ene reaction of allyl sul_des "Equation "03## ð65CJC426\ 82JA213Ł and a retro ð2¦1Ł
cycloaddition "Equation "04## ð74TL4154Ł have also been used to generate thioaldehydes[
∆
S S (14)
S S
S Ph
∆
But But S (15)
N 39%
O Ph
225 Thioaldehydes and Thioketones
2[97[1[0[4 Sulfuration of aldehydes and derivatives
Although the direct conversion of a carbonyl group into a thiocarbonyl group is the most widely
used procedure for the preparation of stable thioketones "see Section 2[97[2#\ it has received little
attention for the synthesis of thioaldehydes[ This may be because the reagents and conditions that
are routinely used are incompatible with these comparatively unstable compounds[ However\
hexamethyl disilathiane "TMS!S!TMS# has been used either on its own ð68ZOB0973Ł\ or in com!
bination with boron trichloride ð71JA2093Ł\ n!butyllithium ð77JA0865Ł\ or cobalt chloride
ð80JOC6212Ł\ to prepare a range of thioaldehydes which could readily be trapped as DielsÐAlder
adducts in good yield[ The n!butyllithium!promoted reaction has also been applied to the dienal
"05#^ the thioaldehyde thus formed undergoes intramolecular DielsÐAlder cyclization "Scheme 00#
ð78SC1320Ł[
H
TMS-S-TMS, BunLi
54%
O S S
H
(16)
Scheme 11
Aldehyde dimethyl acetals can be converted into the corresponding thioaldehydes by reaction
with "Me1Al#1S^ the products were trapped with phosphonium ylides\ to give alkenes in reasonable
yields ð82CE42Ł[
NMe2
Scheme 12
S S
S
S
S
S S S S
(17) (18)
Another potentially versatile method for the formation of thioaldehydes has recently been
described by Dzhemilev et al[ ð81IZV059Ł[ Reaction of the sulfoxide "08# with catalytic Ni"acac#1\
triphenylphosphine\ and triethylaluminum\ in the presence of butadiene gave an 71) yield of the
DielsÐAlder adduct "19# "Equation "05##[ This technique has been applied to a range of dialkyl
sulfoxides\ and a number of alternative catalysts have been described ð80URP0579588\ 81URP0609459Ł[
Given the ready access to a wide variety of sulfoxides\ this method should prove to be applicable to
the preparation of a range of thioaldehydes[
C6H13
i, Cp2ZrCl2. BunLi
S But But
But • ii, 2 equiv. HCl
S + SH
(17)
62%
But But But
40% 60%
A number of photolytic and thermal techniques have been used to generate simple thioaldehydes
for characterization in the gas phase or by matrix isolation[ The 0\1!elimination of hydrogen
chloride from alkylsulfenyl chlorides discussed above has been carried out thermally to prepare
thioformaldehyde ð65JA5943Ł and thioformyl cyanide ð80T3816Ł\ and photolytically to produce
thioacetaldehyde ð80CB1598Ł[ The thermolysis of thiocyanohydrins has also been used to prepare
thioaldehydes ð77TL4788\ 80T3816Ł[ The thermal elimination of sulfur from 0\1\3!trithiolane has been
employed in the preparation of thioformaldehyde ð66CC176Ł[ A range of thermal methods for the
formation of thioaldehydes has been summarized in a paper by Bock et al[ ð71CB381Ł[
A number of synthetic approaches have been described which selectively produce vinyl thiols "the
enethiol tautomers of thioaldehydes#[ These include the addition of hydrogen sul_de to alkynes
ð52JA852\ 54CJC606Ł and the cleavage of vinyl sul_des ð69RTC482\ 60IJS"B#74Ł and vinyl thiocyanates
ð89JCR"S#219Ł[ The vinyl thiols formed\ with the exception of ethenethiol which has a half!life of
between an hour and several days ð66CC372Ł\ were stable enough to be isolated\ although a slow
tautomerization to the corresponding thioaldehyde\ followed by polymerization\ was observed[ For
more details of these methods\ see Chapter 1[03[0[
(21) (22)
Scheme 13
S
Cl
S –HX
SX SX S
• •
Scheme 14
O O
HS
NHPh S
N Ph
S 69%
Se Se
O O
(23)
Scheme 15
A more versatile method for the synthesis of this class of compounds\ in moderate yields\ is a
modi_cation of the VilsmeierÐHaack reaction ð74CC0188\ 78JCS"P0#0130Ł[ Thus\ reaction of enamines
with phosphoryl chloride and DMF or N!methylformanilide\ followed by hydrolysis of the resulting
Vilsmeier salts with methanolic sodium hydrogensul_de\ provided a wide range of stable thio!
aldehydes "Scheme 06#[ Proton NMR data showed that these compounds existed exclusively as the
Thioaldehydes 228
enamino thioaldehyde tautomer\ rather than the alternative imino thioaldehyde or iminovinyl thiol
form ð78JCS"P0#0130Ł[ A related approach has been applied to the synthesis of a diselenovinyl
thioaldehyde ð77JOC2418Ł[
R2 R2 R2
+
POCl3, DMF NaSH
R1 R1 NMe2 R1 S
37–87%
R3R4N R3 R4 N R3 R4 N
Scheme 17
(24) (25)
Scheme 18
+
Ph NH2 Ph
N S
Ph (19)
S 51%
NHMe
(26) (27)
Ph
+
N 3 equiv. Ph NH2
S
(20)
S 39%
Ph NHBn
(28)
Ph 〈84CC1469〉
〈83T1487〉
Ph O S+ CO2Me
∆ 75%
∆ Et3N Ph
S Ph 92% S CO2Me
〈86JOC1556〉 hν LDA 〈85TL5265〉
84% 48% O
O
S
Ph SH
N
Ph TMS-S-TMS, additive
Se
〈8 2JA3104, 88JA1976, 85–96% O
91JOC7323〉 〈87JA5549〉
Ni(acac)2, Ph3P TBDMS-OTf (see also 〈89JOC1092〉)
Ph Et3Al EtNPri2
O
39%
Ph S S8
S
O Et2NH Ph
56% S
〈92IZV160〉 15%
〈90JOC4200〉
∆ 97% CsF 90%
Ph PPh3 Ph SAc
〈88CL1145〉 SAc
Cl
Ph S 〈88JA5452〉
S Ph
Ph S
O S
〈82CC1029〉 TMS
〈85TL1947〉
LDA = lithium diisopropylamide
Scheme 19
Ar S Ar
S NH
Ar
(31)
The only stable thiobenzaldehyde to have been prepared\ isolated\ and fully characterized is the
highly sterically crowded 1\3\5!tri!"t!butyl#thiobenzaldehyde "21#\ synthesized by Okazaki et al[ by
the addition of an aryllithium to ethyl thionoformate "Equation "11## or the sulfuration of hydrazone
"22# "Equation "12## ð71CC0076Ł[ This thiobenzaldehyde is quite stable\ and has been used to study
the reactions of the thioformyl group ð73TL738\ 73TL762Ł[ More recently\ Okazaki and co!workers
Thioaldehydes 230
have prepared deuterated 1\3\5!tri!"t!butyl#thiobenzaldehyde in 26) yield by reaction of the aryl!
lithium with O!cholesteryl deuterothionoformate ð76BCJ0926Ł[ Crossley and Curran reported the
preparation of thioveratraldehyde from the corresponding aldehyde by reaction with H1S and HCl\
but the data presented suggest that this compound was probably not monomeric ð63JCS"P0#1216Ł[
But But
S
Li
OEt S
(22)
56%
But But But But
(32)
But But
HN HN HN
EtNH2, AcOH H2S, NaOMe
HN HN HN
94% 86%
O O O
Scheme 20
Following this precedent\ a number of stable hetaryl thioaldehydes have been prepared using
related methods[ Reid and co!workers have developed a modi_cation of the Vilsmeier reaction
which has proved to be applicable to a number of heterocyclic systems ð55CC390\ 69JCS"C#034\
62JCS"P0#546\ 76KGS0583\ 89KGS0174Ł[ As an example\ reaction of the indolizidine "26# with phosphoryl
chloride and DMF produced the Vilsmeier salt "27#[ This was then treated directly with aqueous
sodium hydrogensul_de to produce the thioformyl indolizidine "28# in 75) yield "Scheme 10#
ð55CC390\ 69JCS"C#034Ł[ A modi_cation of this procedure\ utilizing dimethyl thioformamide in place
of DMF\ has proved to give better results in some cases ð58JCS"C#802Ł[ McKenzie and Reid also
demonstrated that the thioaldehydes could be prepared via an enol ether\ although the thiolysis
only proceeded in 22) yield ð55CC390\ 69JCS"C#034Ł[
Direct sulfuration of heteroaromatic aldehydes has been employed for the preparation of stable
thioaldehydes[ McKenzie and Reid _rst described the reaction of formyl indolizidines with P1S4 as
an alternative to the Vilsmeier synthesis\ the thioaldehydes being formed in good yield "Equation
"13## ð69JCS"C#034Ł[ Becher et al[ have demonstrated that treatment of o!amino heteroaromatic
231 Thioaldehydes and Thioketones
N N 86% N
+
NMe2 S
(37) (38) (39)
Scheme 21
aldehydes with either hydrogen sul_de:hydrogen chloride or Lawesson|s reagent generated the
corresponding stable thioaldehydes "Equation "14## ð80S598Ł[ They also showed that these com!
pounds could be prepared in good yield by the one!pot reaction of o!azido aldehydes with hydrogen
sul_de\ _rst in the presence of piperidine to catalyze reduction of the azide\ then with an excess of
hydrogen chloride to catalyze the thionation of the aldehyde[
P2S5, C5H5N
(24)
N 59% N
O S
Ph O Ph S
H2S, HCl
(25)
N N
N NH2 55%
N NH2
2[97[2 THIOKETONES
Thioketones are generally more stable than the corresponding thioaldehydes[ This is particularly
so for diaryl thioketones in which the C1S electron density is delocalized through both aromatic
rings[ Even the simplest of this class of compound\ thiobenzophenone\ is a relatively stable molecule\
and diaryl thioketones have been known for many years[ However\ simple thioketones which are
not stabilized by electronic or steric factors are still highly reactive compounds which have frequently
been generated and trapped in situ\ or characterized at low temperature or in the gas phase[
One consequence of the greater stability of thioketones than thioaldehydes is that rather more
vigorous methods can be used for their formation without signi_cant decomposition of the products[
This\ combined with the very ready availability of ketones\ means that the predominant method for
the preparation of thioketones is the direct conversion of a carbonyl group\ or a simple carbonyl
derivative\ into a thiocarbonyl[ Various other methods have been used to synthesize thioketones\
but they tend to have been applied to only a few speci_c cases rather than being of general utility[
Early work in this area has been reviewed by Campaigne ðB!55MI 297!90Ł[
HS SH O S
H2S, HCl, –25 °C H2S, HCl, –80 °C
32% 55%
Scheme 22
O S
H2S, HCl, 0 °C
(26)
40%
The reaction is commonly performed in methanol or ethanol\ but co!solvents such as ether can
be used[ Additives such as trialkyl orthoformates have also been employed\ and appear to allow the
reaction to be conducted at higher temperature without the formation of dithiols ð63JCS"P0#0683\
68TL1566Ł[ In the reaction of adamantanone with H1S and HCl in ethanol at −44>C an alternative
product\ the `eminal ethoxythiol "39#\ was formed in reasonable yield ð58CJC2604\ 69CJC2429Ł[ This
was converted into adamantanethione in excellent yield by heating under vacuum "Scheme 12#[
OEt
O S
H2S, HCl, EtOH, –55 °C SH 100 °C, 15 torr
57% 93%
(40)
Scheme 23
When applied to ketones bearing one or more a!hydrogen atoms there is the possibility of the
formation of the enethiol tautomer of the product thioketones[ With simple thioketones the enethiols
are not generally seen ð67RTC010Ł\ although the reaction of naltrexone is reported to give the
corresponding enethiol ð80JMC0181Ł[ The situation with b!oxothioketones is considerably more
complex "see below#[
A somewhat less acidic variant of this technique\ which uses anhydrous zinc chloride instead of
HCl\ has been applied to a series of bicyclic ketones by Vialle and co!workers ð79JOC1406Ł[ The
product formed was dependent on which isomer of the starting material was used\ with some of the
initially formed thioketone products undergoing rearrangement under the reaction conditions[
When applied to diketones this method can yield either monothio or dithio products\ depending
upon the precise conditions used[ Thus\ the monothiodiketone "30# was prepared from the diketone
by reaction with H1S and HCl at −69>C for 1[4 h "Equation "16## ð65TL3186\ 66T2978Ł[ Reaction of
various cyclobutanediones with H1S in the presence of HCl and zinc chloride produced either the
233 Thioaldehydes and Thioketones
dithiones selectively ð60JOC2774Ł\ or a mixture of the mono! and dithiones ð76JOC1043Ł\ depending
upon the exact conditions used[
O O O S
H2S, HCl, –70 °C
(27)
35–65%
(41)
Enolizable b!oxo thioketones can also be prepared by this technique\ thioacetylacetone being
formed from acetylacetone in excellent yield under carefully controlled conditions ð66ACS"B#39Ł[
Interesting selectivity was observed when the same conditions were applied to nonsymmetrical
diketones ð66JOC2012Ł[ 1!Acetylcyclohexanone reacted selectively at the endocyclic carbonyl "Equa!
tion "17##\ whereas the analogous cyclopentanone gave the exocyclic thione as the only product in
low yield "Equation "18##[ The selectivity for the endocyclic carbonyl in cyclohexanones appears to
be general for several substituted compounds ð75JA529Ł[ b!Keto esters ð61T4812\ 63T2642\ 65RTC061Ł\
b!keto thioesters ð57T4212Ł\ b!keto dithioesters ð62BSF"1#0862Ł\ and b!keto lactones and thiolactones
ð58T4692Ł react selectively at the ketone carbonyl to give good yields of the b!thioxo compounds[
These b!oxo thioketones can exist in a number of tautomeric forms\ the relative amounts of which
depend upon a number of factors\ including solvent\ temperature\ and molecular structure[ The
di}erent tautomers can be interconverted by photolysis at suitable wavelengths "Equation "29##
ð68JCS"P1#0421Ł[ This area has been extensively investigated by Duus and co!workers\ who have
studied the tautomerism in detail and proposed a model to explain the observations ð71JA4811\
72JCS"P1#0210\ 75JA529Ł[ A more detailed discussion of this complex area is given in the review of the
thiocarbonyl group by Duus ð68COC"2#262Ł[
O O S O
O O S
O
H2S, HCl, –40 °C
(29)
4.5%
H H
S O hν (353 nm) S O
(30)
hν (288 nm)
Hydrogen sul_de will also react with ketones under basic conditions[ The usual product formed
in this case is the dithiol\ but some ketones give low yields of thioketones "Equation "20##
ð52AG"E#269Ł[ 0\2!Diketones react to give the corresponding monothiodiketones\ predominantly in
the enethiol form\ but 0\1!diketones are reduced to either the a!hydroxy ketone or the monoketone[
O S
S
Pyridine 90 70CJC3530
90 °C, 11 h
S
Pyridine 93 91JOC5932
F 90 °C, 11 h
Pyridine 69 75JCS(P1)2513
S 110 °C, 30 min
O2
S Pyridine 15 83JOC214
110 °C, 3 h
S
DIGLYME, NaHCO3 20 83JOC214
110 °C, 2 h
S
Pyridine 60 (Diels–Alder adduct) 90JCS(P1)3175
EtO2C CO2Et 110 °C, 1 h
As is the case with other reagents\ the reaction of P1S4 with diketones can result in the formation
of either monothio or dithio compounds\ depending upon the conditions used[ Thus the sulfuration
of cyclobutanedione "31# gave either the monothiodione "32# or the dithione "33# as the major
product\ depending on the amount of P1S4 used and the reaction time ð56JOC0451Ł[ A by!product\
the thione "34#\ was formed in one of the reactions "Scheme 13#[ Similar mixtures of mono! and
dithiodiketones have been observed in other systems ð81CJC863Ł[ An interesting example is the
reaction of P1S4 with a 1!keto!0\2!diamide[ The major product from this reaction was the ketodithio!
amide\ but a small amount of thioketone was also produced ð72LA0583Ł[
The preparation of the thioketone "35# has been reported by Lipkowitz and Mundy ð66TL2306Ł[
This compound could be prepared by reaction of the corresponding ketone with P1S4 ð68JOC375Ł\
but was also one of the products formed in the reaction of methyl vinyl ketone with P1S4 in pyridine\
together with a smaller amount of the regioisomer "36# "Equation "21##[ Presumably the reaction
235 Thioaldehydes and Thioketones
initially produces methyl vinyl thioketone\ which then undergoes a DielsÐAlder reaction with
unreacted ketone[
P2S5, pyridine
+ (32)
O O O
S
(46) 13% (47) 1%
Although P1S4 is a versatile reagent for the synthesis of thioketones\ in some circumstances the
conditions required for the reaction to proceed are such that the initially formed thioketone
decomposes or undergoes further reaction[ In this way\ treatment of the diketone "37# with P1S4 in
re~uxing pyridine did not give the desired dithioketone\ but the dithiolactone "38# "Equation "22##
ð72JOC3371Ł[ In contrast\ the dithioketone could be prepared\ in 69) yield\ by using H1S\ HCl\ and
zinc chloride[ A similar rearrangement product was isolated from the reaction of P1S4 with the
cyclobutanedione "31# ð56JOC0451Ł[ Interestingly\ this product could be converted into the desired
cyclobutanedithione "33# by photolysis in nonprotic solvents ð79CC132Ł[
P2S5, pyridine
O O (33)
S
S
(48) (49)
Lawesson|s reagent "49# has also been used for the conversion of ketones into the corresponding
thioketones ð67BSB112\ 79CB1144\ 80TL0676Ł\ and its use has been reviewed ð74T4950Ł[ In some cases\
enethiols can be formed ð71T882Ł\ and di!t!butyl dithiet "40# was formed in the reaction of "49# with
the monothiodiketone "41# "Equation "23## ð71JCR"S#203Ł[ Interestingly\ neither the dithiet "40# nor
the thioketone "41# could be prepared directly from the diketone ð67NJC220Ł[
S S
MeO P P OMe
S S
(50)
OH Cl i, Na2S SH
PCl3 ii, HCl
95%
O O O
(53) (54)
Scheme 25
O OTf S
(TfO)2O Na2S
But But But
70% 82%
PPh3 +PPh PPh3
3
Tf = trifyl
Scheme 26
"ii# Hydrazones
Hydrazones have proved to be useful intermediates in the conversion of ketones into thioketones\
and have found particular application to the preparation of highly sterically hindered thioketones[
The thermal decomposition of triphenylphosphorylidene hydrazones "easily prepared from the
hydrazone itself# in the presence of elemental sulfur was used by de Mayo et al[ to prepare several
thioketones\ in varying yields "Scheme 16# ð67TL3510Ł[ However\ in a number of cases this method
failed\ particularly with enethiolizable compounds[
PPh3
NH2 N
O H2NNH2, ∆ N Ph3PBr2, Et3N N S8, ∆ S
An alternative method which has found wider application to the formation of sterically hindered
thioketones has been developed by Okazaki et al[ ð68TL2562\ 70BCJ2430Ł[ Reaction of hydrazones
with S1Cl1 provides thioketones directly\ probably via an unstable thiosul_ne "44# which eliminates
237 Thioaldehydes and Thioketones
sulfur in situ "Scheme 17#[ The yields of this process are generally good\ and it has been used
to prepare various thioketones as intermediates in the synthesis of hindered alkenes ð72TL4750\
73CB166Ł[
NH2 S
N S2Cl2, Et3N S S
Scheme 28
"iii# Imines
The reaction of N!phenylimines with H1S in the presence of benzoic anhydride provides pure
thioketones in good yield ð64ZN"B#659Ł[ b!Keto thioketones can be prepared from the corresponding
b!keto imines by this method[ The lithium or sodium salts of imines react with carbon disul_de to
form thioketones in good yield[ This method has been applied to the preparation of di!t!butyl
thioketone "Equation "24## ð63JCS"P0#0683\ 64BCJ1392Ł and other hindered thioketones ð66JCR"S#035\
73CB166Ł[
NH i, MeLi S
ii, CS2
(35)
But But 100% But But
"iv# Enamines
Enamines can be converted into thioketones in good yield by reaction with H1S ð59BCJ0632Ł[ This
method can be used to prepare\ in monomeric form\ thioketones "e[g[\ cyclohexanethione# which
tend to form trimers under other conditions[ The reaction has been extended to the synthesis of b!
thioxo esters*in this case tri~uoroacetic acid is used as an additive ð68JOC2160Ł[
CF3
F F3C CF3
S8, ∆ S
Hg CF3 base
S S
60% F3C CF3
F3C CF3 F3C CF3
F
Scheme 29
Thioketones 238
I S
F
F3C P 2S 5 , ∆ F3C
CF3 CF3 (36)
F 92% F
F F
A number of a\a!dioxo thioketones have been generated by the reaction of b!diketones with
dithiobissuccinimide and pyridine[ The resulting thioketones were not stable\ but could be trapped
as DielsÐAlder adducts ð76JOC058Ł[
F S
SH
F3C NaF F3C
CF3 CF3 (37)
F 100% F
F F
(56)
The most widely used variant of the 0\1!elimination technique has been the cycloreversion of 1\1!
disubstituted 0\2!dithiolanes or derivatives\ under basic or pyrolytic conditions[ In general\ the
product from the reaction of a thioketal with butyllithium is the corresponding thiol\ formed by the
reduction of the _rst!formed thioketone by butyllithium ð71JOC2208Ł[ However\ in the case of
camphor thioketal the major product is thiocamphor\ apparently because this thioketone undergoes
deprotonation to form an enethiolate rather than being reduced[ Base!induced elimination from 0\0!
dioxo!0\2!dithiolane "46# has been employed by Schaumann and co!workers to prepare thiocamphor
"Equation "27## ð71AG52\ 72AG"E#44Ł[ Several of the methods used to generate thioaldehydes described
in Section 2[97[1[0[2 have also been applied to the preparation of thioketones "see Scheme 5 and
Equation "09## ð77CB0048\ 89CB066\ 89JOC3199Ł[ A related method\ the reaction of a\a!dibromo!
carbonyl compounds with EtOCS1−K¦\ has been used to prepare reactive a!oxo thioketones which
can be trapped as DielsÐAlder adducts ð64CB562\ 67ZN"B#306\ 70TL1860\ 89JCS"P0#2064Ł[
S LDA
S (38)
S 47%
O O
(57)
i, NaNH2
ii, S
O O S
EtO R2
(39)
R1 R1 R2
An interesting alternative approach has been reported by Hayashi and Midorikawa ð62TL1350\
64JAP"K#6438140Ł[ In this case\ condensation of the anion of ethyl trimethylsilylthioacetate with an
aromatic aldehyde produced the a!thioketo ester "47#\ which existed exclusively as the enethiol form
"48# "Scheme 29#[
Scheme 30
S S
S S S
RCHO NaOH
R R
NH NH
CO2H
O O
(60) (61) (62)
Scheme 31
S SH
Ph NaOMe
O Ph (40)
CO2Me
O
(63) (64)
1!Alkyl 0\2!thiazines undergo hydrolysis under very mild conditions to produce the enethiol
tautomers of b!thioketoamides in reasonable yields ð72CPB0818Ł[
Thioketones 240
"iv# Reduction of sul_nes
In the reaction of di!t!butyl sul_ne with Grignard reagents\ di!t!butyl thioketone was formed\ in
varying yield depending on the Grignard reagent used[ The best result was obtained with
t!butylmagnesium chloride\ which gave 36) of the thioketone ð68JOC1133Ł[ Phosphorus pentasul_de
can also be used as the reducing agent in these reactions ð72CB55Ł[
chloramine T ∆ S
S
50% S S 88%
S
H
H
(65) (66)
Scheme 32
S S S S CN
hν CN
O S O O
85%
S S S S
Scheme 33
An unusual spirocyclic thioketone was obtained as one product from the reaction of a polycyclic
dithietane with triphenylphosphine ð89JA2918Ł\ and an interesting trithiocarbonyl compound was
formed from the reaction of a dithiomalonamide with an azodicarboxamide ð81LA816Ł[ A number
of other rearrangement reactions have given thioketones as products ð66AG"E#611\ 72JA5040\ 80CB0636\
241 Thioaldehydes and Thioketones
82CB62Ł\ occasionally in good yield\ but none appear to be generally applicable[ The electrolysis of
alkenes using a sulfurÐcarbon cathode produces a range of products\ including thioketones\ but
again this technique appears to be of limited synthetic use ð89BSF316Ł[ The photolysis of thiocarbonyl
compounds has been extensively studied\ and in several reactions new thioketones form at least
some of the products[ However\ these reactions appear to be more of theoretical interest than useful
synthetic methods\ and the reader is referred to a review of this work by Coyle for further details
ð74T4282Ł[
The enethiol tautomers of thioketones have been prepared by the cleavage of vinyl sul_des with
alkali metals in ammonia ð69RTC482Ł\ and by the addition of H1S to alkynes ð52JA852Ł[ The reaction
of alkynes with elemental sulfur has been used to prepare a number of 0\1!dithietes\ which appear
to exist in the cyclic form rather than as 0\1!dithiones ð59JA0404\ 50JA2323\ 68H"01#0042\ 82TL004Ł[
H P2S5, RT H
(41)
70%
H H H H
O S
OH
Ph Ph S
P2S5, RT
Ph Ph (42)
Ph 85%
Ph
O
O
Lawesson|s reagent "49# has been employed extensively for the formation of a\b!alkenyl thio!
ketones[ The reaction is generally conducted in toluene at or above room temperature\ and proceeds
in good yield ð71T882\ 89JMC456\ 89SC602Ł[ THF has also been used as the solvent ð81S640Ł[ When
applied to acyclic systems the products are often isolated as dimers ð81MI 297!90Ł[ Davy|s reagent
"56# has been used with some success "Equation "32##^ the dithione can also be prepared by using a
longer reaction time ð80CB0286Ł[ The combination of "TMS#1S and TMS!OTf can be used to
synthesize acyclic and cyclic enethiones in moderate yield ð82TL762Ł[ Thioacetic acid has also been
used as a sulfuration reagent in combination with a strong acid catalyst ð70S25Ł[ The mechanism of
this process is not certain\ although performing the reaction in an alcoholic solvent resulted in the
isolation of a bis"thioester#\ which could then be converted into the thioketone in good yield using
a strong acid in dichloromethane[
O S
Ph Ph (67), PhMe, ∆, 1 h
Ph Ph
(43)
Ph Ph 58% Ph Ph
O O
S S
MeS P P SMe
S S
(67)
A number of other methods have been used for the formation of a\b!alkenyl thioketones\ although
none has found wide application[ As mentioned above\ acyclic thioketones of this type readily
dimerize\ and these dimers have been employed as sources of the monomers by the retro DielsÐ
Alder reaction*the monomers can then undergo further reaction "Scheme 23# ð81MI 297!90Ł[ The
reaction of the ketone "57# with an excess of P1S4 resulted in the formation of the phosphorus!
containing bicycle "58#[ Thermolysis of this compound generated an alkenyl thioketone\ which could
be trapped with dienophiles "Scheme 24# ð71TL0152\ 77CL606Ł[
Ar
O
(50)
Ar [dimers]
35–44% 37–50%
S
Scheme 34
Ando and co!workers have developed a novel Lewis acid!promoted rearrangement of alkenic
episul_des which forms cyclopentenethiones in moderate yield "Equation "33## ð78JOC3559Ł[ They
have also applied a similar rearrangement to the preparation of an allenic cyclobutanethione in low
yield ð78TL3160Ł\ and to other systems ð78TL3714Ł[ A number of other rearrangement processes have
given rise to alkenic thioketones ð79JA5523\ 79NJC692\ 70AG"E#469Ł[
243 Thioaldehydes and Thioketones
Ph Ph
Ph
O CN CN
P2S5, Et3N, CS2 ,∆
But
Ph But 20% P 96%
But S S But S
S
(68) (69)
Scheme 35
S
Ph
S TMS
Ph BF3•Et2O
Ph (44)
Ph 35%
TMS
a\b!Alkenyl thioketones have also been prepared from thioketones by aldol reaction with an
aldehyde followed by dehydration ð54MI 297!90Ł\ but as this reaction does not involve formation of
the thioketone function\ these reactions will not be discussed in detail in this chapter[
NMe2 NMe2
P2S5
O NMe2 S NMe2 (45)
O S
(70)
Another complex area is that of linear multisulfur systems and related compounds[ The simplest
of this class of molecules\ 0\5\5al3!trithiapentalenes\ can be regarded either as bicyclic systems
containing tetravalent sulfur "60# or as a mixture of the isomers "61# and "62# in equilibrium
"Equation "35##[ For the purpose of this review the structure "60# will be taken as the best description
of these molecules\ the synthesis of which is discussed in Section 2[97[3[1[4[ The situation is more
complex with four! and _ve!sulfur systems\ for example "63#\ prepared by the action of P1S4 on the
corresponding ketone "Equation "36## ð60BSF3318\ 66CC740Ł\ the structures of which show signi_cant
SÐS interaction ð69ACS0353\ 60ACS2466\ 62ACS1406Ł[ For a detailed discussion of the structures\ reac!
tivity\ and synthesis of this type of compound\ the review by Lozac|h should be consulted
ð73CHEC"5#0938Ł[
S S S
(71)
S S S S
S S
(46)
(72) (73)
Thioketones 244
S S O S S P2S5 S S S S S
Ph Ph Ph Ph (47)
63%
(74)
Phosphorus pentasul_de has been used to prepare a variety of electronically stabilized thioketones\
including vinylogous thioamides "Equation "37## ð60BAP438\ 78MI 297!91Ł\ doubly vinylogous thio!
amides ð80KGS0321Ł\ and triply vinylogous thioamides "Equation "38## ð70HCA1258Ł[ Compounds
stabilized by the presence of two vinylic heteroatoms have also been prepared by this method
ð71BRP1970694\ 80AG"E#760Ł\ as have various squaramide derivatives ð65S334\ 66CB1495\ 68S250Ł and
cyclopropenethiones ð73AG"E#618Ł[
Me2N O P 2S 5 Me2N S
(48)
22%
O S
P2S5, Et3N
(49)
10%
NPri2 NPri 2
Lawesson|s reagent "49# has been applied to the synthesis of enamino thioketones ð68S830\
76TL5350Ł\ and its use has been reviewed ð74T4950Ł[ The optimum conditions for the formation of
this type of compound appear to be reaction at room temperature with dimethoxyethane as the
solvent\ although heating in toluene has also proved to be e}ective ð81MI 297!91Ł[ A number of
stabilized dithioketones have been prepared by Sandstrom and co!workers by reaction of the
dioxygen analogues with Lawesson|s reagent "Scheme 25# ð80JOC0891\ 80JOC3808Ł[ These compounds
are highly polarized\ with signi_cant electron transfer from nitrogen to sulfur taking place\ and may
be better described by formula "64#\ especially as "65# is reported to have a large twist angle about
the nominal C1C bond ð80JOC0891Ł[ These workers have also developed a sulfur analog "66# of
Lawesson|s reagent which they claim to be more stable and easier to handle ð80JOC0891Ł[
(50)
O O S S S S–
Bn Pri 82% Bn Pri Bn Pri
N N N N N +
N
(76) (75)
Scheme 36
S S
MeS P P SMe
S S
(77)
Ethoxycarbonyl isothiocyanate has been used to prepare monothio derivatives of squaric acid
diamides "Equation "49## ð67S720Ł[ This reaction is unsuccessful for compounds containing free NH
groups\ as in this case heterocycles are formed\ but the reagent may be of wider utility than has
been demonstrated to date[
O O
EtOCONCS, MeNO2
Me2N O Me2N S (50)
54%
NMe2 NMe2
245 Thioaldehydes and Thioketones
Iminium salts can be hydrolyzed e.ciently by reaction with H1S and catalytic amine base to
produce the corresponding thioketone ð67ZOR555\ 68ZOR71Ł[ This reaction has been used in the
preparation of amine!stabilized cyclopropenethiones "Equation "40## ð65S581\ 80CB554Ł and of dithio!
vinyl thioketones ð64JPR026Ł[ The additionÐelimination reaction of vinylic chlorides with sodium
sul_de has also been applied to the formation of cyclopropenethiones ð62JA2932Ł and acyclic
enaminothione "67# "Equation "41## ð80LA000Ł[
+
NMe2 S
H2S, pyridine
(51)
83%
Ph NMe2 Ph NMe2
Cl S
Na2S
+ (52)
Me2N NMe2 60% Me2N NMe2
(78)
A number of the methods described in detail in Section 2[97[1[1[0[ii have been employed to
prepare stabilized thioketones[ Isothiazolium salts can be opened by hydride reagents to give
enamino thioketones in good yield "Equation "42## ð77SC0736Ł^ a similar compound has been
observed as a by!product in the preparation of pentalenes ð68JCS"P0#1239Ł[ The thiazolidine derivative
"68# can be opened with an enaminonitrile to produce the cyclic thione "79# "Equation "43##
ð89JCS"P0#2992Ł[ A closely related reaction has been applied to the synthesis of pyridin!3!thiones
ð73JHC0334Ł[ The cycloaddition reaction of 0\1!dithiole!2!thiones with alkynes has also been suc!
cessfully used for the synthesis of thiocarbonylmethylene dithioles "Equation "44## ð61JCS"P0#30\
79BSF"1#429\ 81MI 297!92Ł[
Et
N+ S NaBH4, –20 °C EtHN S
(53)
90%
S S
Ph NH2 Ph
NC NC
S KOBut,
(54)
N 68% N
S H H
(79) (80)
CO2Me
S S
S DMAD S S
CO2Me (55)
65% S
Et Et
NH2 S S NH2
100 °C
(57)
F3C F3C
Thioketones 246
"iii# Cross!conju`ated electronically stabilized thioketones
Pyridin!3!thiones\ pyran!3!thiones\ and thiopyran!3!thiones are stable thioketones in which the
C1S bond is stabilized by cross!conjugation with the heteroatom lone pair[ These compounds bear
many similarities to the simple electronically stabilized thioketones considered above\ but have been
very widely studied and are thus worthy of separate consideration[
The compounds are most commonly prepared from the corresponding oxo species by reaction
with P1S4[ N!Alkylpyridones have been popular starting materials\ the reaction being performed by
heating in the absence of solvent ð47JCS2509\ 53JCS1659\ 89JAN0049Ł\ in pyridine ð80EUP9351420Ł\ or
xylene ð64JCS"P0#521Ł[ The free NH compounds have also been employed successfully ð80DP038Ł[ A
number of 3!thiopyrones have been prepared^ in this case benzene has been the favoured solvent
"Equation "47## ð40JA299\ 48JCS1477\ 51JCS0746\ 67BCJ068Ł[ 3!Thiothiopyrones have also been syn!
thesized by this method ð56JOC2039Ł[ Silicon disul_de ð64JCS"P0#0224Ł and dimethyl thio!
formamide:acetic anhydride ð81JHC730Ł have been utilized for the conversion of 3!pyrones into
3!thiopyrones[ This transformation has also been achieved via the dichloride "70# "Scheme 26#\ a
method which has been demonstrated to give better results than the direct reaction with P1S4 in
some cases ð47JA5201Ł[ Pyridin!3!thiones have been formed from 3!halopyridines by treatment with
sodium or potassium hydrogensul_de "Equation "48## ð58ACS0864\ 65JOC2673\ 89EUP9265613\ 80CPB561\
80EUP9398053Ł[
O S
P2S5, PhH
(58)
85%
O O
O Cl Cl S
SOCl2 MeCOSH
47%
Ph O Ph Ph O Ph Ph O Ph
(81)
Scheme 37
Cl S
NO2 NH2
NaSH
(59)
66%
H2N N NH2 H2N N NH2
H
3!Thiothiopyrones have been synthesized by the reaction of alkynes with 4!unsubstituted 0\1!
dithiole!2!thiones ð79BSF"1#429Ł or 0\1!dithiole!2!iminium iodides and NaSH "Equation "59##
ð79BSF"1#428Ł[ This latter process may occur by rearrangement of a _rst!formed trithiapentalene\ as
it has been shown that these compounds rearrange to the thiopyran!3!thiones upon treatment with
NaSH or Na1S ð57CC752Ł[ Reductive ring opening of a suitably substituted dithiolium salt with
potassium borohydride gave a 3!thiothiopyrone as the _nal product\ formed by cyclization of the
intermediate enamino thioketone ð70TL3496Ł[
S
S S MeCCNEt2, NaSH
+ (60)
Ph NEt2 55%
Ph S NEt2
The cycloaddition of diphenyl cyclopropenethione with heterocycles has been utilized as a con!
venient synthesis of pyridin!3!thiones ð62CC722\ 63T3914\ 64JCS"P0#521\ 65JOC707Ł[ This reaction pre!
sumably involves initial 0\2!dipolar cycloaddition to give the intermediate "71#\ which then fragments
with loss of carbon oxysul_de to give the observed product "Scheme 27#[ Other heterocycles have
also been shown to undergo fragmentation and rearrangement to produce pyridin!3!thionesð73H"11#652\
73JHC0334Ł[ Alternative condensation reactions have produced 3!thiopyrones ð80EGP183830Ł and
247 Thioaldehydes and Thioketones
3!thiothiopyrones ð65TL3172Ł\ but these appear to be limited in their applicability[ Pyridin!3!thiones
can be formed in reasonable yield from the corresponding 3!thiopyrones by reaction with ammonia
ð67BCJ068Ł[
Me S
Ph S N Ph Ph
O S
S +
20%
N+ O– S N Ph
Me Ph Ph Ph Ph
Ph Me
(82)
Scheme 38
720 °C
S
S 690 °C S
O
S
S
540 °C
(83)
S
S O
S
Scheme 39
O
S S S
S S
S
hν S S hν S
O
S S S hν S
S S
S S S
O
(84) (85) (86)
Scheme 40
S, 150 °C
(61)
57%
N2 S
(88) (87)
o!Thiobenzoquinone methide "78# has been generated by photolysis of a dithiole dioxide "89#
ð67JOC2263Ł or a retro DielsÐAlder reaction ð80TL1902Ł\ but is more commonly produced by ther!
molysis of benzothiet "80# ð75TL4692Ł[ The compound has been characterized from photolysis of
"80# in an argon matrix ð78JST"087#296Ł\ but cannot be isolated\ and has been trapped as DielsÐAlder
adducts ð76AG"E#0935\ 89CB0032\ 80JHC462Ł or a ð3¦3Ł dimer "81# "Scheme 30#[ o!Thiobenzoquinone
methides stabilized by a dithiole ring have been prepared by the photolytic reaction of benzodithiole!
thione "82# with alkenes ð63CC766\ 63CL0328Ł^ these compounds cannot be obtained pure\ but exist
in equilibrium with their head!to!head dimers "83# "Scheme 31#[ The monomers can be trapped by
the DielsÐAlder reaction with dienophiles ð66CJC2652\ 68BCJ385Ł[ The related thionaphthoquinone
methide "84# has been prepared\ and is a stable monomer "Equation "51## ð65TL2704\ 71BCJ132Ł[
Thiobenzoquinone methides bearing nitrogen and oxygen\ as well as sulfur\ stabilizing groups have
also been prepared ð68BCJ2539\ 71LA03Ł[ A nitrile!substituted thiobenzoquinone methide has been
postulated as a decomposition product of an azidobenzothiophene\ and has been trapped with
alkenes ð74CC0330Ł[
O H O
O N Ph
S N Ph
S O hν
O S
(90) H O
43%
S
∆
(89) S
S
S
(91) (92)
Scheme 41
S S S
S
S S
, hν S
S
90%
S S S S
(93) (94)
Scheme 42
S S
S
S cyclohexene, hν
(62)
S 100% S
(95)
259 Thioaldehydes and Thioketones
2[97[2[1[1 Thioketones bearing an a\b!aryl or hetaryl substituent
The chemistry of diaryl thioketones has been thoroughly explored\ and the early work in this
area has been reviewed ðB!55MI 297!90\ 62IJS062Ł[ Alkyl aryl thioketones are in many cases similar\
although less stable\ and the same methods of preparation can be applied as to diaryl compounds[
The synthesis of these compounds is discussed in Section 2[97[2[1[1[iv[ Aryl thioketones bearing an
a\b!alkenyl bond are generally more closely related to the alkenic compounds covered in Section
2[97[2[1[0 than to other aryl thioketones\ and will be covered separately in Sections 2[97[2[1[1[iÐiii[
Thioanthraquinones and naphthoquinone methides\ although strictly aryl thioketones\ have been
discussed with their benzo analogs in Section 2[97[2[1[0[iv[
Ph
∆
Ph S SPh
SPh SPh 78%
Ph (99)
(50) SPh
CO2Me
46% S
Ph O Ph S ,∆ SPh
(97) (98) 56% CO2Me
Ph S
Scheme 43
S
O O
Na2S, S8, NaOH
O O (64)
O 65% O
(100) (101)
O O
S CO2Me
S DMAD, ∆
(65)
64%
S CO2Me
S
S S
S S 290 °C S S
(66)
+
Ph N 90% N
Ph
Ph Ph
Me
S S NHMe
,∆ S N
MeHN
(67)
Ph S 62%
Ph N
Me
N ArCHO, S8, ∆ S HN
(68)
5–38%
N Ar N
Me Me
O S
P2S5, Na2CO3
(69)
N 96% N
H H
O S
Ph (50), ∆ Ph
(70)
68%
AcO O Ph AcO O Ph
O S
P2S5, pyridine
(71)
75%
OH O O
(102)
This type of compound can also be formed by the reaction of chloro compounds with NaSH
"Equation "61## ð49JOC599\ 65JOC2673\ 67JOC3809Ł or thiourea ð49JOC599\ 55TL5288\ 78MI 297!93Ł[ The
reaction of H1S with 8!amino derivatives of acridine has been employed for the preparation of
acridine!8!thione ð37JCS0070Ł[ Xanthane dichloride has been converted into xanthane thione in
excellent yield by reaction with EtOCS1−K¦\ followed by basic hydrolysis ð57CB605Ł[ Other reported
methods include the cyclization of the enamine "092# to produce the thione "093# in good yield
"Equation "62## ð80JHC0134Ł\ and the cleavage of dialkyl thioquinanthrenes with H1S to form
quinoline thiones ð81H"23#136Ł[
Cl S
N N
N N
N NaSH, DMF N
EtO2CNH N EtO2CNH N (72)
H
HO 65% HO
O O
OH OH OH OH
S O S
O
SMe
Ph2O, ∆
(73)
N 76% N
H H
(103) (104)
O (50) S
N N (75)
Ph NMe2 50% Ph NMe2
Ph OO Ph Ph XY Ph Ph S Ph S S
Ph Ph
(50), PhMe, ∆ S
S + (76)
+
62%
68% (X = Y = S) 3% 8%
21% (X = S, Y = O)
As described in Section 2[97[2[1[1[i above\ the sulfuration of simple alkenyl aryl ketones results
in the formation of DielsÐAlder dimers "88#\ which are themselves alkyl aryl thioketones[
"b# Sulfuration of aryl ketone derivatives[ A number of carbonyl derivatives have been converted
into aryl thioketones[ The Vilsmeier approach developed by McKenzie and Reid for the preparation
of heteroaryl thioaldehydes can also be applied to thioketones "Scheme 33# ð55CC390Ł[ The reaction
of imines with carbon disul_de has also been shown to produce diaryl thioketones in good yield
ð58TL2500\ 69T706Ł^ dimethylthioformamide can be used in place of carbon disul_de\ although the
yields are lower ð58TL2500Ł[ The hydrolysis of enamines with H1S has been used for the preparation
of b!oxo ð68JOC2160Ł and b!thioketo ð61IJS"A#105Ł thioketones[ The reaction of hydrazones with
S1Cl1 has also been demonstrated to produce thiobenzophenone ð68TL2562\ 70BCJ2430Ł\ but it gives
rise to cyclic adducts when applied to the monohydrazone of a diketone "Equation "66##\ presumably
by intramolecular trapping of the intermediate thiosul_ne ð81CC6Ł[ An interesting reaction is the
cycloaddition of diphenyldiazomethane with the thioketone "094#\ which gave thiobenzophenone
and the episul_de "095# as products ð80MI 297!90Ł[ These products presumably arise from the two
di}erent orientations possible for the cycloaddition "Scheme 34#\ or\ in the case of "095#\ by the
cyclization of a thiocarbonyl ylide[ Diaryl thioketones can also be prepared from the corresponding
`em!dichlorides by reaction with "TMS#1S ð61ZOR0711Ł or with t!butyl thiol and TFA ð67BSB112Ł[
The reaction of a phosphonium ylide with cyclic polysul_des "see Section 2[97[1[0[5# has been used
to form ~uorene thione\ although this compound was trapped as a DielsÐAlder adduct rather than
being isolated ð80S674Ł[ Diaryl thioketones can also be prepared by the oxidative sulfuration of
the corresponding diarylmethanes ð18CB2937\ 34JCS747Ł or aminodiarylmethanes ð91CB264Ł with
elemental sulfur[ The reaction of a polycyclic ethoxy compound with NaSH produced the cor!
responding thioketone ð74S528Ł[ A related additionÐelimination approach has been applied to the
preparation of phosphonium ylide!stabilized aryl thioketones "see Scheme 15\ But Ph# ð81TL4844Ł[
253 Thioaldehydes and Thioketones
dimethylacetamide
POCl3 NaSH
N N+ 66% N
Me2N S
Scheme 44
NH2
O N S S
Ph Ph S2Cl2, Et3N Ph Ph
O (77)
56%
Ph
Ph S N2
S
But +
N Ph Ph But TMS
Ph2CN2 N
TMS
S
But TMS
Ph2CN2
(105)
S N S
But
N But Ph + N2
TMS
Ph Ph TMS Ph
(106)
Scheme 45
"c# Formation of the a C0C bond[ Phosphonium ylide!stabilized aryl thioketones have been
synthesized by the condensation of methylene triphenylphosphorane with methyl dithiobenzoate
ð64BCJ1896Ł[ A sulfoxonium ylide!stabilized aryl thioketone has been prepared by a similar route
involving the reaction of dimethylsulfoxonium methylide with thiobenzoyl chloride "see Equation
"019## ð65BCJ2017Ł[ The reaction of Grignard reagents with chloro dithioformates did not produce
the expected dithioesters\ and instead thioketones were formed[ A possible mechanism for this
reaction\ involving initial thiophilic attack by the Grignard reagent\ has been proposed "Scheme 35#
ð64RTC0Ł[ Symmetric thioketones can be prepared by the FriedelÐCrafts reaction of electron!
rich aromatics ð0784CB1758Ł or heteroaromatics ð58AJC128Ł with thiophosgene "Equation "67##[
Thiobenzoyl chlorides can also be used in this reaction to give mixed thiobenzophenones in reason!
able yields ð57CB2406Ł[ By direct analogy with the preparation of other b!oxo thioketones\ the
condensation of enolizable ketones with O!alkyl thiobenzoates has been used to synthesize a wide
range of b!oxo aryl thioketones ð54AG"E#043\ 66JCS"P0#0016\ 66S145\ 74S561Ł[
S
PhMgBr EtS Ph
S S
S EtS–
PhS PhS
Ph Ph
EtS Cl PhMgBr EtS 31%
Cl SEt
SPh
–
EtS Cl
Scheme 46
CSCl2
(78)
N N N
H H S H
Thioketones 254
"d# 0\1!Elimination reactions[ The 0\1!elimination reaction "see Section 2[97[1[0[2# has been used
extensively for the formation of aryl thioketones[ Bunte salts have been widely employed as the
starting materials\ base!catalyzed elimination giving rise to a variety of a!oxo aryl thioketones\
including monothiobenzils ð68CB1633\ 79JHC0544\ 70LA09Ł[ In some of these reactions the initially
produced thioketones were unstable and rapidly formed dimers ð64TL426\ 66JCR"S#133\ 66JOC1710\
73JOC3641Ł[ 0\1!Elimination reactions from thiocyanates ð55CC475Ł\ phenyl disul_des ð57CC613\
69JCS"B#214Ł\ a!chlorosulfenyl chlorides "Equation "68## ð68JOC0625Ł\ and thiosulfonates ð74JOC21Ł
have been used to prepare diaryl thioketones[ The product of the reaction between `em!dichlorides
and EtOCS1−K¦ undergoes 0\1!elimination upon treatment with aqueous alkali to give diaryl
thioketones in excellent yield ð57CB605Ł[ The reaction of thioacids with imines ð48MI 297!90Ł\ oximes\
and nitrones ð66BCJ1640Ł gives rise to addition products which spontaneously undergo 0\1!elim!
ination to produce diaryl thioketones in good yield[
Cl S
SCl Ph3P
Ph Ph (79)
Ph Ph
72%
O O
A number of 0\2!dithiolane derivatives have also been used to generate alkyl aryl and diaryl
thioketones by 0\1!elimination "or cycloreversion# ð71AG52\ 72AG"E#44\ 77CB0048\ 89CB066\ 89JOC3199Ł*
these methods have been discussed in detail in Section 2[97[2[0[2[i[ An interesting reaction of this
general type is the reaction of dithioketals with tungsten hexacarbonyl[ This process usually gives
alkenes by coupling of two molecules of the dithioketal\ but in highly hindered systems thioketones\
postulated to be intermediates in the coupling reaction\ can be isolated in modest yield ð89JOC0763Ł[
"e# Reduction of sul_nes[ Thermolysis of thiobenzophenone S!oxide produces small quantities
of thiobenzophenone ð66ACS"B#568Ł[ A much more e}ective technique for this reduction has been
developed by Zwanenburg and co!workers\ who demonstrated that P1S4 or PSBr2 reduces a variety
of diaryl sul_nes to diaryl thioketones in excellent yield ð70S184Ł[ This technique\ combined with a
number of methods for the preparation of sul_nes that do not involve thioketone oxidation\ make
this a practical synthetic method for the preparation of thioketones[
"f# Other methods[ A number of cycloreversions and related reactions have been used to syn!
thesize aryl thioketones[ Kusters and de Mayo have prepared the substituted dithiobenzil "096# by
photolysis of "097# "Equation "79##[ Compound "096# was found to exist mostly as the dithione\ not
the tautomeric dithiet ð62JA1272Ł[ It was not possible\ however\ to prepare the unsubstituted parent
compound by this method ð63JA2491Ł[ An attempt to prepare acenaphthenedithione by the same
method did not lead to the desired product\ although it could be trapped by the DielsÐAlder reaction
with dienophiles ð74JOC0449Ł[ The thio!Claisen rearrangement of allyl "0!arylvinyl# sul_des has been
successful in forming alkyl aryl thioketones ð61CC51\ 78CPB0888Ł[ As the starting material can be
made by S!allylation of thioketones\ this technique provides a method for the C!allylation of
aryl thioketones[ The dimers of aryl thioketones\ such as monothiobenzil\ can undergo ð1¦1Ł
cycloreversion to generate the monomeric compound on heating or irradiation ð79ZN"B#261Ł[
Me2N Me2N
S S
hν
O (80)
50%
S S
Me2N Me2N
(108) (107)
An interesting formation of an aryl thioketone is the reaction of the sulfoxide "098# with tosyl
isocyanate to produce "009#\ an imino analog of monothiobenzil "Equation "70## ð74JOC0096Ł[
O S
TsNCO
S Ph (81)
Ph
28%
Ph Ph NTs
(109) (110)
255 Thioaldehydes and Thioketones
Aryl hetaryl thioketones can be prepared by forming the heteroaromatic ring\ as in the synthesis
of thiobenzoyl thiophenes developed by Mollier and co!workers involving cyclization of a diene
nitrile with elemental sulfur "Equation "71## ð60CR"C#167\ 63BSF"1#360Ł[ The diene nitrile can be formed
in situ by the reaction of cinnamaldehyde with ethyl cyanoacetate[
CO2Et
CO2Et
CN Et3N, S8, 100 °C
S (82)
63% S NH2
Ph
Ph
Several photolytic syntheses of aryl thioketones have been reported "Equations "72# ð56JA1682\
69JOC3113Ł\ "73# ð61CC521\ 62JCS"P0#0479Ł\ and "74# ð63ZC06\ 73JOC0726Ł#\ although these have not been
generalized[ Photolytic ð61TL4102Ł or cathodic ð63AG"E#238Ł reduction of a 2\4!diphenyldithiolium
salt gives rise to dithiobenzoyl methane[
O S
O O hν
S Ph (83)
Ph
56%
Ph Ph
Ph Ph O
Ph S OH
S hν
(84)
Ph But
37%
Ph O But Ph
S O
hν S
Ph N Ph NH (85)
95% Ph
O Ph
The enethiol tautomer of b!oxo aryl thioketones has been prepared by the Michael addition of
thioacetic acid to aroylphenylalkynes ð54LA"571#077Ł[ Elemental sulfur can be added to phenylalkynes
to provide the dithiet isomers of alkyl phenyl a!dithiones ð82TL004Ł[
A number of other reactions have produced aryl thioketones ð65TL1850\ 73AG"E#799\ 77JPR24\
89TL6530\ 82CB62Ł\ but none appear to be of general synthetic utility[
– +
S S
(111) (112)
Given the wide range of compound types which fall within the scope of this section\ it is impossible\
in the available space\ to give a fully comprehensive account of all the preparative methods that
have been used[ This survey will attempt to give a brief summary of the key synthetic methods for
each compound type\ and also refer to important reviews and other leading references from which
more detailed information can be obtained[ For the many heterocycles which will be mentioned\ it
is recommended that Comprehensive Heterocyclic Chemistry be consulted for a more detailed
consideration of the synthesis and properties of these compounds[
In the sections below\ the compounds will be divided according to the coordination state of the
sulfur atom[ Within each section\ simple compounds will be discussed _rst\ followed by heterocycles
containing a C1S bond[
Ph S Ph
H2CN2, –78 °C S –45 °C Ph S
Ph >95%
Ph N N Ph
(113)
Scheme 47
Me2N S CN Me2N S CN
+ –
Me2N CN Me2N CN
(114)
257 Thioaldehydes and Thioketones
CN CN
Pri2N S Pri2N S
I CHCl3, ∆
Ph
+ CN (86)
CN 86%
NPri2 NC Pri2N NC
The preparation\ properties\ and reactions of thiocarbonyl ylides have been reviewed ð61JOC3934\
65T1054\ 68COC"2#262Ł[
2[97[3[0[1 Sul_nes
Sul_nes\ or thiocarbonyl S!oxides\ are well!studied compounds\ and many stable examples have
been prepared[ By far the most widely used method for the synthesis of sul_nes is oxidation of the
corresponding thioketone[ The oxidation of thioketones by molecular oxygen is a reaction of
considerable mechanistic interest\ and has been the subject of detailed investigation\ notably by
Ramamurthy and co!workers ð71JOC016\ 72JOC103Ł[ Of more importance as a preparative method is
the use of peroxy acids or hydrogen peroxide as the oxidant[ m!Chloroperoxybenzoic acid is the
most commonly employed\ and in general good yields are obtained "Equation "76## ð62JCS"P0#62Ł[
A report has extended the scope of this reaction to enethiolizable thioketones ð80TL636Ł[ Mono!
peroxyphthalic acid has also proved to be an e}ective oxidant ð66LA0418Ł[ In these reactions the
conditions must be carefully controlled to avoid over!oxidation and formation of the ketone
ð69JOC0605\ 60JCS"B#0436Ł[ A similar problem is encountered when ozone is used as the oxidant\
although this method is e}ective for the preparation of sterically hindered sul_nes ð62S506Ł[ Dimethyl
dioxirane has also been used with some success ð80JCS"P0#2932Ł[
S S
mcpba O
(87)
75%
A conceptually di}erent approach is the alkylidenation of sulfur dioxide[ This can be achieved
by the reaction of SO1 with phosphonium ylides "Equation "77## ð67TL796Ł\ or by a Peterson reaction
using an a!silyl carbanion[ The latter approach may be more versatile\ as the silyl component can
be readily prepared by silylation of an active methylene compound\ the overall reaction proceeding
in good yield "Scheme 37# ð67TL700Ł[ An alternative approach to the generation of the anion is by
addition of a nucleophile to a vinyl silane\ although the yields for this method are generally rather
lower ð67TL2272Ł[ In situ generated sulfur monoxide will also react with ylides to produce sul_nes\
although the yields are very substrate!dependent ð68JCS"P0#0619Ł[ The reaction between sulfur mon!
oxide and diazoalkanes also generates sul_nes in modest yield ð58TL3350\ 65CC320Ł[
O
PPh3 S
SO2, PhH, 60 °C
(88)
80%
O
TMS S
i, BunLi i, BunLi
ii, TMS-Cl ii, SO2
80%
O O O
Scheme 48
The base!promoted elimination of HCl from sul_nyl chlorides was one of the earliest methods
used for the synthesis of sul_nes "Equation "78## ð53JA0780Ł[ More recently\ a convenient one!pot
approach for the preparation and elimination of the sul_nyl chloride has been described "Scheme
38# ð73CC491\ 73TL4836\ 78T2630\ 81CJC853Ł[ This 0\1!elimination approach\ analogous to that widely
employed for the formation of thioaldehydes\ has been extended to other types of substrate and has
been the subject of extensive study by Kice and co!workers ð80JOC0313\ 80JOC0320Ł[ A novel variant
Further Substituted on Sulfur 258
of this method is the elimination of chloroform from allyl or benzyl trichloromethyl sulfoxides to
produce vinyl or aryl thioaldehyde S!oxides "Equation "89## ð83TL842Ł[
Cl O O
S S
Et3N
(89)
75%
O-TMS O O
SOCl2 Cl
S S
48%
O O
Scheme 49
O DABCO O
Ph S Ph S (90)
CCl3 95%
DABCO = 1,4-diazabicyclo[2.2.2]octane
The retro DielsÐAlder reaction of a variety of precursors has been employed to prepare a!oxo!
and a!iminosul_nes "Scheme 49# ð77CB722\ 89JCS"P0#2064\ 89TL4614\ 80NJC422\ 80PS"48#308Ł[ The thio!
Claisen reaction of allyl vinyl sulfoxides is a rapid reaction leading to the formation of sul_nes in
excellent yield "Equation "80## ð74JA5620\ 80JCS"P0#2088\ 81JOC2019\ 81SL898Ł[ Retro cyclization of a
dithiolane trioxide has also been used to prepare sul_nes ð89CB066Ł[
Ph
Ph
PhMeN O Ph
O S RT
PhMeN + S PhMeN O
O N S
O N 96%
O
Tol Tol
Scheme 50
O O
S 0 °C S
(91)
98%
Ph Ph
Many simple sul_nes are unstable and have either been generated and trapped in situ or char!
acterized in the gas phase[ This is particularly true of sul_ne itself\ which has been the subject of
detailed study[ The usual way of generating sul_ne and simple analogs is the retro ð1¦1Ł cyclization
of a suitable precursor "Equation "81## ð65JA0153\ 71JA2008\ 89JST"127#60Ł^ this type of reaction has
been reviewed ð71AG"E#114\ 73CHEC"6#338Ł[
500 °C S
S S O O (92)
A number of other approaches have given rise to sul_nes\ although none has been widely used[
These include the oxidation of certain thiophenes with singlet oxygen ð69TL680Ł or peroxy acids
ð89CB1954Ł\ and the desilylation of alkyltrimethylsilylsul_nes to produce thioaldehyde S!oxides\
which are di.cult to prepare by other routes ð75CC853\ 89JOC2633Ł[ For further details of these and
other methods for the formation of sul_nes\ the many reviews of the area should be consulted
ð56AG"E#096\ 69QRS68\ 68COC"2#262\ 71RTC0\ 78PS"32#0Ł[
269 Thioaldehydes and Thioketones
2[97[3[0[2 Thiosul_nes
In contrast to their oxygen analogs\ thiosul_nes are highly reactive species which have so far
eluded isolation[ However\ there is considerable evidence for their existence\ from both mechanistic
arguments and trapping experiments ð76JA891\ 81CC300\ 81CC599Ł[ For a discussion of the chemistry
of these transient species\ other reviews should be consulted ð78PS"32#52\ 89SUL72Ł[
O O
S Cl
S
ButNH2 NBut
Cl (93)
73%
N
TMS i, BunLi S Ar
ii, ArNSO
(94)
76%
HClO4
+
71% +
S S S S
50% 50%
Scheme 51
The related thiophenium ions can be formed by the direct protonation of thiophenes with
~uorosulfonic acid ð62TL2818Ł[
The peracetic acid oxidation of 0\1!dithiole!2!thiones is also a widely used technique "Equation
"85## ð50JA1823\ 57CJC0744Ł[ Acid!promoted cyclization of thioketones bearing a suitably positioned
thiocyanate group has proved to be a useful method for the formation of a range of fused ring
dithiolium salts "Equation "86## ð89JCS"P0#1770Ł[ Dithiolium salts can also be formed by the ring
opening of trithiapentalenes and related compounds\ brought about by protonation ð64JCS"P0#1986Ł
or alkylation ð57JOC1804Ł[
S S S+ S
MeCO3H
Ph Ph (96)
S
61%
S SCN S+ S
HClO4
(97)
93%
MeO OMe MeO OMe
X
Y S
Z
(115)
Ph Ph Ph Ph Ph Ph Ph Ph Ph
N N
S S MeN S S S PhN S S S O S
N N N N
Ph Ph Ph Ph Ph Ph Ph Ph
(116) (117) (118) (119) (120) (121)
The most widely utilized method for the preparation of this class of compound is the reaction of
a diketone with P1S4 "Equation "87## ð63JA3157Ł[ This reaction is versatile and has been employed
in the synthesis of many nonclassical thiophenes[ An alternative\ somewhat milder\ technique is the
dehydration of sulfoxides\ usually with acetic anhydride "Equation "88## ð58JA2841Ł[ The early work
in this area has been reviewed ð64ACR028Ł^ more recent reviews are provided in Comprehensive
Heterocyclic Chemistry ð73CHEC"3#0926\ 73CHEC"5#0916Ł[
Ph
Ph Ph Ph
O P2S5, pyridine
S S S (98)
O 83%
Ph Ph Ph
Ph
Ph Ph Ph Ph
Ac2O
S S O S S (99)
87%
Ph Ph Ph Ph
The analogous six!membered ring system has been prepared in 72) yield by the reaction of a
diketone with P1S4 in pyridine ð58JA2842Ł[
+
S S
(122) (123)
A number of methods have been employed for the formation of sulfonium ylides\ the most widely
used\ especially for unstabilized ylides\ being deprotonation of the corresponding sulfonium salt[
The base used depends upon the type of ylide being formed[ For stabilized ylides\ weak bases such
as triethylamine are generally used[ For simple sulfonium ylides\ stronger bases are required\ and
the precise choice of base and reaction conditions can be critical for the successful formation of the
ylide ð56TL1214Ł[ A number of modi_cations to the conditions for deprotonation have been
suggested\ including the use of heterogeneous reaction conditions ð76T2834Ł and a polymerically
supported reagent ð68TL192Ł[
Another versatile method for the formation of sulfonium ylides is the reaction of a diazo com!
pound with a sul_de under photolytic\ thermal\ or metal!catalyzed conditions "Equation "099##
ð61JOC0610Ł[ A wide range of structural types have been prepared by this method\ including
cyclopentadienylides ð56CI"L#007Ł\ thiophenium ylide "013# "Equation "090## ð67CC72\ 68JCS"P0#1513Ł\
dicyanomethylidene ylides ð65LA530Ł\ and cyclic ylides "Equation "091## ð76TL260Ł[ Some early
examples of this technique have been reviewed by Ando ð61IJS"B#078\ 66ACR068Ł[
Me Me Me Me
N2 S , hν S
(100)
88%
MeO2C CO2Me MeO2C CO2Me
N2 thiophene, Rh2(OAc)4
S (101)
MeO2C CO2Me 93%
MeO2C CO2Me
(124)
O O
CO2Et CO2Et
Rh2(OAc)4
(102)
N2 67% S
Ph
SPh
Stabilized sulfonium ylides can also be prepared from the corresponding active methylene com!
pounds by reaction with sulfoxides\ or ethoxysulfonium salts\ under a variety of conditions "Equa!
tion "092## ð56T3168Ł[ The yields for this process are generally modest\ although in some cases\
which appear to be substrate!dependent\ better results have been obtained ð57JA639Ł[ Various
modi_cations to the method have been reported to give improved yields ð67S567Ł[ b!Hydroxy
ketones can be directly converted into diketosulfonium ylides by oxidation in the presence of DMSO
"Equation "093## ð72JOC0888Ł[ A similar result has been obtained using the CoreyÐKim reagent
"014# ð77S067Ł\ and this reagent has also been used to convert active methylene compounds into
dimethylsulfonium ylides in good yields "Equation "094## ð78CL862Ł[ Active methylene compounds
can be transformed into vinylic sulfonium ylides by reaction with a base and an enaminosulfonium
salt "Equation "095## ð68CB2996Ł[
O Ph
S
S
Ph Me , Ac2O, 100 °C
(103)
44%
O O O O
263 Thioaldehydes and Thioketones
S+ N
O
(125)
S
Ph (125), Et3N
Ph (105)
O O 96%
O O
+
S EtO2C CN, NaH NC S
(106)
Me2N 70%
CO2Et EtO2C CO2Et
The addition of a nucleophile to a vinyl! or polyvinylsulfonium salt has been used to prepare
several sulfonium ylides "Equation "096## ð62TL3922\ 64TL1974Ł[ A number of other techniques have
given rise to sulfonium ylides\ but none has received wide application ð69CPB389\ 63TL0960\ 64JOC2746\
66CL614Ł[ Sulfonium ylides can also be functionalized to form more complex sulfonium ylides by
alkylation\ acylation\ or other processes "Equation "097## ð57JOC2406\ 69TL4186\ 63BCJ898\ 64CC178\
65JCS"P0#0577Ł[
O O
S+ N S
piperidine
(107)
S MeO2C S
O MeO2C
DMAD
(108)
100% O
A number of reviews have discussed the synthesis and properties of sulfonium ylides ðB!55MI 297!91\
B!64MI 297!90\ 68COC"2#136Ł[
Several S!aminosulfonium ylides have also been prepared\ either from an active methylene
compound ð65S209\ 67ZOR0548Ł or from a thioketone S!imide ð63JOC1774Ł[ An interesting reaction
is shown in Equation "098#\ although it is not clear whether this could be developed into a general
method ð80ZOR106Ł[
O
SAr
– NBS Ar N
S (109)
CO2Et
O
O CO2Et
O
Further Substituted on Sulfur 264
There are a number of species that are structurally related to sulfonium ylides\ notably the anions
of sul_limines and sulfoxides[ These species are almost exclusively formed by deprotonation and
reacted in situ\ although it is possible to isolate the anions if required ð79JA1359Ł[ They will not be
considered further here[
2[97[3[1[1 Sulfenes
Sulfenes\ or thiocarbonyl S\S!dioxides\ have been the subject of intense study[ However\ despite
this interest\ no stable sulfene has yet been isolated[ They have been prepared and trapped in situ\
and are implicated as intermediates in several common reactions^ for example\ the reaction of a
base and methanesulfonyl chloride is believed to generate sulfene\ which then reacts with alcohols
to form mesylates[ A number of experiments have been reported in which sulfene has been generated
and studied in the gas phase or at low temperature ð58CJC3498\ 60JA5293\ 63JA1853Ł[
Tertiary amines interact with sulfenes generated by base!induced elimination of HCl from sulfonyl
chlorides ð65CJC1541Ł\ but it is not clear whether the adduct is a zwitterion "015# or the sulfene
interacting noncovalently with the amine "016# "Scheme 41#[ However\ Sundermeyer and co!workers
have reported the isolation of an adduct between bis"tri~uoromethyl#sulfene and quinuclidine
"Equation "009## ð78AG"E#110\ 89CB484Ł[ The x!ray crystal structure of this adduct suggests that the
SÐN interaction is relatively weak and the C0S bond has considerable double bond character[
R3N O R3N – O O
Ph SO2Cl Ph S Ph S + Ph S
NR3
O O O NR3
(126) (127)
Scheme 52
O O F3C O
S quinuclidine
F3C CF3 S N (110)
F3C CF3 74% F3C
S O
For a detailed examination of sulfene generation and chemistry the review by King and Rathore
should be consulted ðB!80MI 297!91Ł[
O O OMe
SCl
S
NaOMe OMe
Cl (111)
71%
A number of metal complexes of thioaldehydes and thioketones have been reported in which two
metal atoms are coordinated to the thiocarbonyl sulfur[ A discussion of the structure and formation
of these complexes is beyond the scope of this review^ for an example and further references a paper
by Werner and Paul should be consulted ð73AG"E#47Ł[
2[97[3[1[3 Thiabenzenes
Thiabenzenes\ and their polycyclic analogs\ are an interesting class of compounds which bear
many resemblances to simple sulfonium ylides[ Much of the early work in this area\ which involved
the preparation of thiabenzenes by the addition of phenyllithium to thiopyrylium salts\ has been
265 Thioaldehydes and Thioketones
called into question by the detailed studies of Mislow and co!workers ð63JA4537\ 63JA4549\ 63JA4540\
64JA1607Ł and by Hortmann et al[ ð63JA5008Ł[ However\ this technique can\ in some circumstances\
be successfully applied to the synthesis of thiabenzenes and 1!thianaphthalenes ð64JA1607Ł[ A much
more widely applicable method is the deprotonation of thiinium salts "Equation "001## ð64JA1607Ł[
Thiabenzenes are somewhat unstable\ and tend to undergo decomposition or rearrangement readily[
However\ they can be stabilized by the presence of electron!donating groups on sulfur ð65JA2504Ł\
or electron!withdrawing groups on carbon ð67TL140\ 79JOC1357Ł[ The chemistry of thiabenzenes has
been reviewed ð73CHEC"2#774\ 76YGK121Ł[
NaOMe
(112)
S+ 37% S
Me Me
Ar Ar
An example of a four!membered analog\ a thiacyclobutadiene\ has been reported ð63TL2800Ł[
(128)
The starting materials for many syntheses of these heterocycles are 0\1!dithioles or derivatives[
The reaction of a 0\1!dithiole!2!thione with an alkyne\ described in Section 2[97[1[1[0[ii as a method
for the synthesis of electronically stabilized alkenyl thioaldehydes\ also produces variable amounts
of trithiapentalenes[ In general the yields of pentalenes are low\ but this depends on the substrate
structure ð65BSF"1#019Ł\ and alteration of the reaction conditions can also result in a higher yield of
the bicyclic system ð67ZOR1348Ł[ 4!Alkyl!0\1!dithiolium salts react with dimethyl thioformamide in
acetic anhydride or phosphoryl chloride to produce Vilsmeier salts[ When treated with NaSH these
are hydrolyzed and cyclize to form trithiapentalenes "Scheme 42# ð57JCS"C#1432\ 58JCS"C#802Ł[
A related approach is the preparation of enaminodithioles\ followed by hydrolysis "Scheme
43# ð69JCS"C#0191Ł[ Acylmethylenedithioles\ available by a similar route\ can be converted into
trithiapentalenes by reaction with P1S4 in pyridine ð52JA2133\ 53CI"L#350Ł[ Related approaches
can be employed to give trithiapentalenes directly from dithiolium salts ð63CR"C#682\ 63JCS"P0#611Ł[
Diazadithiapentalenes are also prepared from 4!alkyl!0\1!dithiolium salts\ by coupling with arene
diazonium salts "Equation "002## ð65JCS"P0#117Ł[
+ +
S S S S S S S
Me2N NaSH
Me2NCHS, POCl3
59%
Scheme 53
+ S S S
S S N + N KSH Ph
+ S S
Ph Cl
Ph
Scheme 54
Further Substituted on Sulfur 266
Ar
+ S S N
S S ArN2+
N (113)
90–99%
Various structural types can be formed by the cyclization of appropriate precursors "Equations
"003# ð63JCS"P0#131Ł and "004# ð68JCS"P0#1239Ł#[ This method for the formation of these compounds
has been exploited in the conversion of one ring system into another[ Thus\ in several cases\
substitution reactions on the heterocycles are accompanied by rearrangement to produce an alter!
native heterocyclic system "Equation "005## ð63JCS"P0#611\ 65JCS"P0#779Ł[
Me Me
Me
+ SMe N S N
N S MeNH2
(114)
50%
Me
Me
+ OH N S O
N S Na2CO3
N N (115)
87%
O S S O S S
NaNO2
Ph N Ph (116)
60%
OHC
Scheme 55
O S O S S
S
P 2S 5
Na2S (dil.), K3Fe(CN)6
O O
O O
O
(130) (131)
S O
S O S
O Na2S (conc.), K3Fe(CN)6
O
O
(129)
Scheme 56
267 Thioaldehydes and Thioketones
Trithiapentalenes and derivatives have also been prepared from acyclic precursors[ Thus\ 0\2\4!
triketones\ upon reaction with P1S4\ undergo sulfuration and cyclization to trithiapentalenes
ð52JA2133Ł[ The bisoximes of b!diketones react with SCl1 or S1Cl1 to produce a mixture of diaza!
pentalenes "Equation "006## ð61TL0724\ 68BSF"1#088Ł[ The use of S1Cl1 favors formation of the dithia
compound "021#\ whereas the dioxa compound "022# is the major product from the reaction with
SCl1[ Bishydrazones react under the same conditions to produce tetraazathiapentalenes in reasonable
yield ð68BSF"1#194Ł[ Trithiapentalenes have also been prepared from acylalkynes by reaction with
thioacetic acid ð54LA"571#077Ł[
OH OH O S S O S O
N N N N N N
SCl2 or S2Cl2
+ (117)
(132) (133)
Related systems containing four or _ve sulfur atoms in a linear array have also been prepared[
They are commonly made by sulfuration of a ketone\ either directly "see Equation "36## or with
rearrangement "Equation "007## ð60BSF3318\ 66CC740Ł[
O
S S S S S S S S S
But But P2S5
But But (118)
Me
Me O
N2 DMSO, CuSO4 S
(119)
CO2Et 50–65% CO2Et
A widely employed method for the preparation of sulfoxonium ylides is the elaboration of
dimethylsulfoxonium methylide[ This simple ylide can be acylated by reaction with ketenes or
anhydrides\ or carbamoylated with isocyanates[ These reactions can also be combined to give doubly
functionalized ylides "Scheme 46# ð54CB2622Ł[ Thiocarbonyl!stabilized ylides can also be prepared
"Equation "019## ð65BCJ2017Ł[ Dimethylsulfoxonium methylide will also undergo Michael addition
to activated alkynes ð55TL0676Ł\ and additionÐelimination reactions "Equation "010## ð63JCS"P0#0014\
63JOC2064Ł to produce vinylic ylides in moderate yields[ The reaction with imidoyl and related
Further Substituted on Sulfur 268
chlorides has been successfully applied to the synthesis of a number of sulfoxonium ylides "Equation
"011## ð66JCS"P0#0085\ 77CB0994Ł[
Me Me Me
Me O Ac2O
Me O PhNCO Me O
S S S
80% NHPh
O O O
Scheme 57
Me Me
Me O PhCSCl Me O
S S (120)
30% Ph
O O
O
O
+ S Me (121)
Me 28% S
Cl Me Me
O
N N O
+ S Me (122)
Me 52% S
N Cl Me N Me
A number of other species bear close structural and chemical similarities to sulfoxonium ylides[
Anions derived from sulfones can be regarded as containing a C1S double bond\ and have been
widely used in synthesis[ They are generated by deprotonation of the sulfone\ and are almost
invariably reacted in situ without isolation[ The anions produced by deprotonation of sulfoximines
have also proved to be useful reagents\ their reactivity being similar to that of sulfoxonium ylides
ð80TL0164Ł[ They are reasonably stable in solution ð62JA3176Ł\ and have been used in a number of
synthetic applications[ These reagents are again formed by deprotonation of the precursor with a
strong base and reacted immediately[ Their use has been pioneered by Johnson\ who has reviewed
the area ð62ACR230\ 74MI 297!90Ł[
Many metal complexes of sulfur ylides have been prepared\ and although the precise nature of
the bonding in many of these species is unclear\ in some cases a C1S bond may\ at least nominally\
be present[ This area of chemistry has been reviewed by Weber ð72AG"E#405Ł[
Ph Ph
Me
Ph Me NaOMe
+ S O
69% 84% S
O Me S
O Me O
Me O
Scheme 58
O
O
Me
Me
+ S (124)
33%
O
EtO O S
Me O
Scheme 59
F
P2O5 O glass, 270 °C
HO2C SF5 • SF5 SF4
70% 50% O
(136) (135)
Scheme 60
Copyright # 1995, Elsevier Ltd. All R ights Reserved Comprehensive Organic Functional Group Transformations
3.09
Seleno- and Telluroaldehydes
and -ketones
FRANK S. GUZIEC, Jr and LYNN J. GUZIEC
New Mexico State University, Las Cruces, NM, USA
2[98[0 OVERVIEW 270
2[98[1 SELENOALDEHYDES "SELENALS#\ RHC1Se 271
2[98[1[0 Simple Selenoaldehydes 271
2[98[1[1 Metal!stabilized Selenals 275
2[98[1[2 Conju`atively Stabilized Selenals 277
2[98[2 TELLUROALDEHYDES "TELLURALS#\ RHC1Te 278
2[98[3 SELENOKETONES "SELONES#\ R1C1Se 280
2[98[3[0 Simple Selones 280
2[98[3[1 Metal!stabilized Selones 285
2[98[3[2 Resonance!stabilized Selones 287
2[98[4 TELLUROKETONES "TELLONES# 399
2[98[0 OVERVIEW
Despite a number of early reports describing the synthesis of selenium and tellurium analogues
of simple aldehydes and ketones\ the preparation of well!characterized derivatives of these classes
of compounds only dates from the mid!0869s[ Careful examination of the earlier reports suggests
that researchers were initially often led astray by signi_cant limitations in analytical techniques[ The
desired seleno! and tellurocarbonyl compounds were often unstable under the preparative conditions
used and decomposed during the attempted synthesis[ In many cases dimeric and trimeric derivatives
of the desired compounds were obtained\ adding to the confusion[ The early di.culties associated
with the attempted preparation of seleno! and telluroaldehydes and !ketones have been reviewed
ðB!62MI 298!90Ł[
Despite these early problems\ advances in methodology in the late 0879s\ and the introduction of
a variety of novel reagents\ have made these seleno! and tellurocarbonyl derivatives much more
common[ It should be noted that\ in general\ these classes of compounds are not stable enough to
be isolated at room temperature unless the seleno! or tellurocarbonyl functional group is shielded
sterically\ is stabilized by complexation to a metal center\ or is conjugated in a vinylogous manner
to other stabilizing functions[ A number of reviews concentrating on aspects of the preparation and
reactions of seleno! and telluroaldehydes and !ketones have been published ðB!75MI 298!90\ B!76MI
298!90\ B!76MI 298!91Ł[
Finally\ the di.culties associated with the nomenclature of seleno! and tellurocarbonyl analogues
of aldehydes and ketones should be noted[ The terms selenoaldehyde\ selenoketone\ telluroaldehyde\
and telluroketone in the literature often refer to carbonyl compounds with selenium or tellurium
substituents[ Better terms for these compounds are selenal\ selone\ tellural\ and tellone\ respectively[
270
271 Seleno! and Telluroaldehydes and !ketones
It should also be noted that the terms selenone and tellurone are occasionally used incorrectly in
the literature to describe selenium and tellurium analogues of ketones[ These names\ in fact\ refer
to the selenium and tellurium analogues of sulfones[ The detailed nomenclature of seleno! and
tellurocarbonyl compounds has been discussed ðB!76MI 298!91Ł[
O R –H2O Se Se
H+
+ H2Se SeH
R HO R Se R
R = H, alkyl, aryl, (1) R = H
(2) R = Me
(3) R = Ph
Scheme 1
R Se R
FVP Se
(1)
Se Se
1000–1100 K
R
R
R = H, Me
Selenoformaldehyde "0# has also been generated as a transient species by reaction of methylene
with a selenium mirror "Scheme 1# ð57CC348Ł or by FVP of dimethyl selenide "Equation "1##
ð73JA4395Ł[ Irradiation of selone "3#\ isolated in an argon matrix by pyrolysis of a selenadiazole\
a}orded propyneselenal "4# which was characterized spectroscopically "Scheme 2# ð74JOC432Ł[
H Se
CH2N2 [CH2] + Se Se
Se Se
H
(1)
Scheme 2
FVP H
Me2Se Se + CH4 (2)
700 °C H
Selenoaldehydes 272
N FVP hν
Se
N • • Se
Se 700 °C [1,3]-shift
Scheme 3
Despite the extreme reactivity of unstabilized selenals\ they can be readily prepared as transient
species\ and these intermediates trapped as DielsÐAlder adducts "6# by ~uoride!induced elimination
of cyanide from a!silylselenocyanates "5# "Scheme 3# ð75JA0203Ł[ This was the _rst general\ con!
venient preparative method for selenals[ In this procedure an aldehyde is treated with phenyl!
dimethylsilyllithium and the intermediate alkoxide is trapped with p!toluenesulfonyl chloride[
Treatment of the resulting a!silyl tosylate with potassium selenocyanate a}ords the required
a!silylselenocyanate[ DielsÐAlder adducts of the intermediate selenals are isolated in 28Ð78) yield
"Table 0#[
O i, PhMe2Si– Li+ SiPhMe2 KSeCN SiPhMe2
SiPhMe2 Bun4N+ F – Se Se
R SeCN R
R
(6) (7)
Scheme 4
The _rst stable isolable selenal\ 1\3\5!tri!t!butylselenobenzaldehyde "7#\ was prepared using the
above mentioned a!silylselenocyanate method ð78JA4838Ł[ This selenal is a reasonably stable blue
crystalline compound\ which in solution is very sensitive to oxygen even at low temperatures
"−49>C#\ rapidly a}ording the corresponding aldehyde under these conditions[ The selenocarbonyl
compound is also quite reactive\ undergoing thermal cyclization to the benzoselenane "8# at 69>C
"Equation "2##[ This cyclization con_rmed the intermediacy of the selenal "7# in the reaction of tri!
t!butylphenyllithium with hindered selenoformates "Scheme 4# ð75CC60Ł[
But
But
Se
70 °C
But (3)
Se
But But
(8) (9)
273 Seleno! and Telluroaldehydes and !ketones
But But
Se Se But
But Li + But
But Se
O
But But
But
(8) (9)
Scheme 5
K2SeSO3 I2 SO2Cl2
RO2C Br RO2C SeSO3K RO2C Se Se CO2R
H2O–ROH H2O, EtOH benzene
(10) (11)
R = Me, Et
O
O
N K
RO2C SeCl O Se N
RO2C
O
(12)
Scheme 6
O
Et3N Se Se
Se N
RO2C RO2C CO2R
O
(12) (13) (14)
R = Me, Et Scheme 7
Another route to the generation of monomeric selenal intermediates involves the thermal reaction
of a Wittig reagent with selenium in an inert solvent "Scheme 7# ð76TL5538Ł[ Stabilized Wittig species
such as "04# react with elemental selenium at elevated temperatures a}ording intermediate unstable
selenals "05#\ which further react with "04# ultimately leading to the corresponding symmetrical
alkenes[ The intermediate selenals can also be trapped by dienes\ a}ording the corresponding DielsÐ
Alder adducts[
MeO2C
Ph3P toluene Se (15)
+ Se + Ph3P Se
CO2Me 105 °C
CO2Me
74% CO2Me
(15) (16)
Scheme 8
Selenoaldehydes 274
These reactions also proceed with unstabilized alkyl!substituted ylides "Scheme 8# ð77JA513Ł[ The
selenal anthracene DielsÐAlder adducts "06# are particularly interesting compounds since\ upon
mild thermolysis\ the selenals can be regenerated by retrocyclization and trapped by other reagents
"Scheme 09#[
R
Se
PPh3 90 °C
Se
+ Se
21%
R R
R = Ph, Et, Bun (17)
Scheme 9
Se
–
Se Se
75 °C
R R
(17)
R = Ph, Et, Bun, Ph
Scheme 10
A number of reagents have been developed in the 0879s which can be used to introduce selenium
into molecules directly\ converting a carbonyl group into a selenocarbonyl moiety[ Bis"trimethylsilyl#
selenide "07# reacts with aldehydes in the presence of a catalytic amount of n!butyl lithium to
generate a selenal which can be trapped in a variety of ways "Scheme 00# "Table 1# ð77JA0865Ł[ The
driving force for the reaction is the large energy di}erence between the selenide "07# and its oxygen
analogue disiloxane[
O BunLi (cat.) Se
Se O Se
+ TMS TMS + TMS TMS
THF 45–85%
R R
(18) R
Scheme 11
Appropriately substituted selenals can be generated using this method and trapped intra!
molecularly in a DielsÐAlder process "Scheme 01# ð77TL5854Ł[
Bis"dimethylaluminum# selenide "08# is reported to react with acetals to a}ord selenals which can
be trapped with Wittig reagents to a}ord the corresponding alkenes "Scheme 02# ð82CE42Ł[
Trimethylselenophosphate "19# reacts with v!H!per~uoroalkanals to a}ord the corresponding
selenals which can be trapped under normal conditions "Scheme 03# ð80ZOR397Ł[
275 Seleno! and Telluroaldehydes and !ketones
( )n ( )n ( )n
BunLi (cat.)
+ Se
TMS TMS
O THF Se Se
R R R
Scheme 12
(Me2Al)2Se R2
OMe PPh3 R1
(19) R1
R1
Se
OMe R2
O Se Se O
H + P H + P
(CF2)n MeO OMe (CF2)n MeO OMe 49–52%
OMe OMe
n = 4, 6 (20)
Se
H
(CF2)n
Scheme 14
Ph Ph
(CO)5W Se + 2 But (CO) [ But ]2 W Se (5)
The metal complexes can react spontaneously in solution with elimination of the selenal to a}ord
related bimolecular metal complexes "12# "Equation "5## ð74JOM"178#C10Ł[ Fischer et al[ have utilized
the ability of these metal complexes to act as a stable source of selenals in order to carry out a
variety of synthetic transformations of transient selenal species under very mild conditions ð76CC448\
77JOM"247#118\ 78CC556\ 78JOM"253#044\ 89JOM"273#294\ 81CC452Ł[
Selenoaldehydes 276
CO CO
CO CO
– + – +
OC M Se OC M Se
:
OC C6H4R OC
CO CO
C6H4R
(E)-η1 (Z)-η1
CO
CO Se
OC M
OC H C6H4R
CO
η2
Scheme 15
W(CO)5
2 (CO)5W Se (CO)5W Se H Se
+ (6)
R R R
Some formal metal complexes of selenoformaldehyde "13# and "14# can be prepared by dis!
placement reactions on diiodide complexes "Equations "6# and "7## ð72AG"E#205\ 73AG"E#47Ł[ The latter
complex can also be prepared by extrusion of carbonyl selenide from an osmiumÐdiselenocarbonate
complex "Equation "8## ð72JOM"133#C42Ł[
I
NaHSe Se
CpLRh CpLRh (7)
I
L = Me3P (24)
I
NaHSe
L2(CO)2Os L2(CO)2Os (8)
Se
I
(25)
O –COSe
L2(CO)2Os L2(CO)2Os (9)
∆ Se
Se Se
(25)
The electron!rich osmium methylene complex "15# reacts with elemental selenium to form the
selenoformaldehyde complex "16# "Equation "09## ð72JA4828Ł[ Selenoformaldehyde can also act as
a bridging ligand in organometallic complexes[ Reactions of the selenium complexes "17# or "18#
with diazomethane a}ord the bridged complex "29# "Scheme 05# ð72AG"E#203Ł[
L L
NO Se NO
Os Os (10)
Cl Cl Se
L L
(26) L = PPh3 (27)
277 Seleno! and Telluroaldehydes and !ketones
M
Se CH2N2 Se CH2N2 M
Se
M Se
M M –N2 –N2
M
(28) (30) (29)
M = (η−C5Me5)Mn(CO)2, (η-C5H5)Mn(CO)2
Scheme 16
R R
P2Se5
(11)
N O N Se
Me Me
(31)
Other related stabilized selenals "21#Ð"23# can be prepared from heterocyclic amines by a VilsmeierÐ
Haack transformation followed by sodium hydrogen selenide treatment "Equation "01##
ð68JCS"P0#1223Ł[ These selenal compounds can also be prepared from the corresponding formyl
derivatives by treatment with phenylselenophosphonic dichloride "24# "Equation "02## ð77CC0383Ł[
R R R R
Cl +
R i, NMe2 PO2Cl2– R
R R (12)
N ii, NaHSe N
R R
28–46%
R R
Se
R = H, alkyl (32)
Se
R S R S
N N
Se
(33) (34)
Se
R2 R3 Ph
P
Cl
R2 R3
Cl
R1 R1
(35)
R4 R4 (13)
N 62–81% N
CHO Se
Telluroaldehydes 278
The _nal class of stabilized selenals includes compounds which formally contain a selenocarbonyl
moiety in a contributing resonance form such as "25#\ but which are probably better described as
hypervalent sulfur "26# or selenium "27# species ð60JCS"C#2076Ł[ Compounds of this type can be
prepared by selenation of the corresponding aldehyde using phosphorus pentaselenide ð55JA4934Ł\
or more e.ciently by using phenylselenophosphonic dichloride "24# "Scheme 06# ð77CC0383Ł[ The
unsubstituted derivative "27# can be prepared via a displacement and oxidation sequence "Scheme 07#
ð60JCS"C#2076Ł[
Se
P
Ph Ph Cl Ph
Cl Ph Ph
(35)
Ph
Ph Ph Ph
S O S Se S S S
S S Se S Se
(36) (37)
Scheme 17
Se
i, Na2S
ii, Se2–
Se S
Se Se S
iii, K3Fe(CN)6 Se S Se
S Se
(38)
Scheme 18
H Te
Te + CH2 Te (14)
H Te Te
(39) (40)
Ph Te Ph Te
PPh3 Te 11%
toluene
105 ° Ph
(41) (42)
Scheme 19
Bis"dimethylaluminum# telluride "32# acts as an e}ective direct tellurating agent for the prep!
aration of tellurals from the corresponding aldehydes[ The transient intermediate tellurals can be
289 Seleno! and Telluroaldehydes and !ketones
Ph
Te PPh3
Ph
Ph Ph
+ Ph3P Te
PPh3 cat. Te
Ph
100 °C
61%
100 °C
Ph3P Te Ph3P + Te
Scheme 20
trapped as their DielsÐAlder adducts "Scheme 10# ð78JA7638Ł[ The key tellurating agent bis"dimethyl!
aluminum# telluride "32# can be readily prepared via transmetallation of bis"trimethyltin# telluride
"Equation "04## ð78JA7638Ł[ It should also be noted that bis"trimethylsilyl# telluride "33# was not an
e}ective tellurating reagent\ in contrast to its selenium analogue "07# which acts as a convenient
selenating agent "cf[ Scheme 00#[
O OAlMe2 Te
dioxane –(Me2Al)2O Te
(Me2Al)2Te + R
44–62%
R TeAlMe2 R R
Scheme 21
toluene
Bu3SnTeSnBu3 + 2Me3Al (Me2Al)2Te + 2Bu3SnMe (15)
90 °C
(43)
(Bu3Si)2Te
(44)
A number of metal complexes of tellurals have also been reported[ The tungsten pentacarbonyl
complex of tellurobenzaldehyde "34# can be prepared by tellurium insertion into the metal carbene
complex "Equation "05## ð80JOM"304#100Ł[ These complexes have structures analogous to the selenal
complexes previously mentioned "cf[ Scheme 04#[ Thermolysis of "34# a}ords the free tellural as a
transient species which can be trapped by dienes "Scheme 11#[
(CO)5WTe ∆ Te Te
(45) Ph
Scheme 22
A number of formal complexes of telluroformaldehyde have been reported[ Treatment of the m2!
tellurium complex "35# with diazomethane a}ords the bridged complex of telluroformaldehyde "36#
"Equation "06## ð72AG"E#203Ł[
Selenoketones 280
M H
M CH2N2 Te (17)
Te
M M –N2 H
M
(46) (47)
M = (η−C5Me5)Mn(CO)2, (η-C5H5)Mn(CO)2
The electron!rich osmium complex "37# also reacts with elemental tellurium to a}ord the osmium
complex of telluroformaldehyde "38# "Equation "07##[ Finally\ the diiodorhodium complex reacts
with sodium hydrogen telluride to a}ord the telluroformaldehyde complex "49# "Equation "08##
ð72AG"E#205Ł[
L L
NO Te NO
Os Os (18)
Cl Cl Te
L L
(48) L = Ph3P (49)
I
NaHTe Te
CpLRh CpLRh (19)
I
L = PMe3 (50)
SeH [O]
R R
Se + Se Se
R R R R
(52)
Scheme 23
The _rst preparation of a monomeric selone\ not stabilized by metal complexation or resonance
interactions\ involved thermolysis of a phosphoranylidene hydrazone "42# in the presence of selenium
powder "Scheme 13# ð64CC428Ł[ The required phosphoranylidene hydrazones are readily available
by treatment of a hydrazone with triphenylphosphine dibromide in the presence of a tertiary amine
base ð50CB1366Ł[ As well as the selone\ molecular nitrogen and triphenylphosphine selenide are also
formed[ The method remains a general one for the preparation of sterically hindered stable selones
ð65CC194\ 65JCS"P0#1968\ 65JPC0890\ 79JOC1789\ 70TL3452\ 71JOC2452Ł[ Less hindered ketones such as
benzophenone and camphor do not a}ord selones under these conditions[ Instead\ only the
corresponding diazo compound decomposition products and dimeric alkenes are obtained
ð65JCS"P0#1968Ł[ These products can also predominate in more hindered cases if the reaction con!
ditions are not carefully controlled[
The phosphoranylidene hydrazone reaction probably occurs via the reaction of an intermediate
diazo compound "43# with a reactive form of selenium[ If the reaction temperature is too high\ diazo
compound decomposition occurs[ If the selone cannot be readily removed from the reaction mixture\
281 Seleno! and Telluroaldehydes and !ketones
But But N PPh3 But
Et3N Se (excess)
NNH2 + Ph3PBr2 N Se + N2 + Ph3P Se
But But But
(53) 29–75%
Scheme 24
a cycloaddition reaction of the diazo compound with the selone can occur as the latter is formed\
a}ording the alkene via a twofold extrusion reaction[ Attempts at preparation of selones via direct
reaction of diazo compounds with selenium were generally limited by this process "Scheme 14#
ð74T3732Ł[
N2
N PPh3
∆ Se
N N2 Se
(54)
+ Se + N2
Scheme 25
Generally\ a more convenient method for the preparation of sterically hindered selones involves
the reaction of the hydrazone with selenium"I# bromide in the presence of triethylamine "Scheme 15#
ð73JOC078Ł[ A related alternative route uses the hydrazone dimagnesium salt with selenium"I#
chloride ð72CC0318\ 77BCJ750Ł[ Both reactions presumably involve nitrogen extrusion from an inter!
mediate N!selenonitrosimine "44#[ Again\ no selones could be obtained from unhindered ketones[
N Se N
2Et3N –N2
NNH2 + Se2Br2 N N Se
68%
Se
(55)
Scheme 26
Aryl selones such as "45# and "46# are less stable than hindered aliphatic selones[ They can be
prepared using a modi_ed selenium"I# chloride route "Equation "19## ð81CL1178Ł[ The attempted
preparation of selones from the hydrazone "47# failed\ a}ording the cyclic di! and triselenides "59#
and "50#[ These are presumably formed via reactions of the intermediate selone "48# "Scheme 16#[
H2NN Ph Ph NNH2 Ph Se Se Ph Ph Se O Ph
Bun3N, PhH
+ Se2Cl2 + (20)
The reaction of fenchone with bistricyclohexyltin selenide "51# and boron trichloride is reported
to a}ord selenofenchone "53# in 89) yield[ It is believed that this reaction proceeds via a non!
aggregated form of boron selenide "52# "Scheme 17# ð71JA2093Ł[ A comparison of the above methods
for the preparation of stable sterically hindered selone has been compiled ð74T3732Ł and is sum!
marized in Table 2 ð74T3732\ 77BCJ750Ł[
A useful method for the in situ generation of selones involves base!promoted elimination of HCN
from selenocyanates[ This route proved convenient for preparation of an intermediate seleno!
Selenoketones 282
H2NN Ph Ph NNH2 Ph Se Se Ph
Se2Cl2 Se2Cl2
(58) (59)
Ph Se Ph Ph Ph
Se Se
Se + Se
(60) (61)
Scheme 27
But a 29–(75)
1 Se b 65
But c 58
a 75
2 Se b 80
c 82
a 53
3 Se b 70
a 54
4 Se b 68
c 18
a 40
5 Se b 73
a 25
Se b 76
6 c 24
d 90
Se
7 c 53
Se
8 But c 43
a Via phosphoranylidene hydrazone–selenium pyrolysis.b Via selenium(I) bromide–hydrazone.c Via selenium(I) chloride–hydrazone
dimagnesium salt.d Via bis(tricyclohexyltin) selenide.e Isolated yields of purified products.
283 Seleno! and Telluroaldehydes and !ketones
Se
(C6H11)3Sn Sn(C6H11)3 + BCl3 [B2Se3]
Se 90%
Scheme 28
~uorenone "54# which could be trapped as its DielsÐAlder adduct "Scheme 18# ð76TL2776Ł[ The
method has been extended to the preparation of a variety of selones containing electron!withdrawing
substituents "56# "Table 3#[ The key selenocyanate intermediates "55# can be readily prepared via
displacements on the corresponding halides "Scheme 29# ð77JA7568Ł[
Et3N
98%
Se
SeCN Se
(65)
Scheme 29
X SeCN Se
KSeCN Et3N Se
R2
R1 R2 R1 R2 R1 R2
(66) (67) R1
Scheme 30
A number of other methods previously described for the generation of transient selenals can also
be used for the preparation of selones[ Wittig reagents react with elemental selenium to a}ord
transient diarylselones "57# which readily dimerize to the 0\2!diselenacyclobutane "58# "Scheme 20#
ð89AG"E#0956\ 80CL0942Ł[ The dimer is in equilibrium with the monomeric selone in solution[ The
intermediate selone can be trapped by dienes or reduced to the corresponding diselenide "Scheme 21#
ð76TL5538Ł[ The selone also reacts with dimethyl acetylenedicarboxylate to a}ord the heterocyclic
derivatives "69# and "60#[ The alkene generated by reaction of the selone with the Wittig reagent is
also observed "Scheme 22# ð81TL0222Ł[
Selenoketones can also be prepared by reactions of ketones with selenating agents[ Although
bis"trimethylsilyl# selenide "07# was a useful reagent for selenating aldehydes "cf[ Scheme 00#\
selenation failed in the case of ketones[ Bis"dimethylaluminum#selenide "61#\ however\ proved to be
an e.cient reagent for the preparation of selones "Scheme 23# ð78TL1984Ł[ A variety of aryl and
alkyl derivatives could be prepared using this method "Table 4#[
Hexa~uoroselenoacetone "64# can be prepared as an unstable deep purple oil via pyrolysis of the
Selenoketones 284
Ph Ph Ph Se Ph
PPh3 + 2Se Ph3P Se + Se
Ph Ph Ph Se Ph
(68) (69)
Scheme 31
Se
Ph
Ph
Ph i, NaBH4
Ph Ph
Se Se Se
Ph ii, O2 Ph Ph
Se
Ph
Ph
Scheme 32
Ph
Ph PPh3 Ph Ph
Sen
Ph
Ph
PPh3 Se + Ph3P Se
Ph Ph Ph Ph
MeO2C CO2Me
Ph Ph Ph
Ph
Se
+ Se
CO2Me
CO2Me
CO2Me MeO2C
(70) (71)
Scheme 33
O Se
Se
toluene
+ (Me2Al)2Se
reflux 53%
(72)
Scheme 34
1 77
Se
2 63
Se
3 53
Se
4 55
Se
5 44
Ph
Se
6 72
Ph TMS
a Isolated yields of selone Diels–Alder adducts with cyclopentadiene.
F3C Se CF3 KF
+ HgF2 Hg[SeCF(CF3)]2
F3C Se CF3 DMF
100 °C
(73) (74)
Et2AlI
∆
F3C
Se
F3C
(75)
Scheme 35
F3C
CF3
F3C F F3C
CsF
+ Sen Se Se
F F DMF F3C
(76) (77)
Scheme 36
"Equation "10## ð72ZN"B#0254Ł[ Similar to the selenal metal complexes\ these complexes behave as if
the selone moiety retains true selenocarbonyl character ð76CC448Ł[
Ph Ph
A number of stable metal complexes of selenium analogues of b!diketones have been prepared[
Complexes such as "79# can be prepared in situ by reactions of b!diketones such as acetylacetone
with hydrogen selenide in the presence of metal ions "Equation "11## ð58AJC780Ł[ Related complexes
can be prepared via displacement reactions on activated vinyl halides "Equation "12## ð63ZC177Ł or
via a selenation sequence using selenourea "Scheme 27# ð64ZC55Ł[ An uncomplexed b!diselone "71#
has been prepared by ring opening of the selenopyrone "70#\ but exists primarily in its dienediselenol
form "72# "Scheme 28# ð51G748Ł[
O O HCl Se Se
+ NiCO3 Ni (22)
H2Se
Se Se
(80)
Ph Ph
Ph Ph Se Se
+ NaHSe + Ni(OAc)2 Ph Ni Ph (23)
Cl CHO O O
Se Ph
O
O Se H2O
Ph + H2N NH2 NH2
Ph
Ph HN
Ph Ph
H
Se Se
O Se M2+
M
O O
Ph Ph
Ph Ph
Scheme 38
Metal!promoted cleavage of the 0\1!diselenatene derivative "73# also a}ords the metal seleno!
carbonyl complex "74# "Equation "13## ð56CC569\ 69IC0719Ł[ Spectroscopic studies indicate that this
complex may have signi_cant diselone character[
287 Seleno! and Telluroaldehydes and !ketones
Se
Se Se O SeH SeH O
H2O
+ Na2Se
O
(81) (82) (83)
Scheme 39
M = Mo, Ni, W
Cl Se
Substituted selenoacridones "76# can be prepared from the corresponding acridones by a similar
sequence "Scheme 39# ð28CB0135Ł[ N!Substituted selenopyridones such as "77# can be prepared in a
similar manner "Scheme 30# ð93LA134Ł[
+
O Cl
K2SeSO3, H+
+ POCl3 + [PO2Cl2]–
N N
R R
+
SeSO3H Se
hydrolysis
N N
R R
(87)
Scheme 40
Selena!g!pyrone derivatives such as "78# can be prepared from the corresponding thiones by an
alkylationÐdisplacement sequence "Equation "15## ð46AC"R#0133\ 66CC066Ł[ Related compounds such
as "89# can also be prepared via halogenationÐselenation\ similar to the method used to prepare
selenoacridines "Equation "16## ð60JCS"C#2076Ł[
Selenoketones 288
O Cl Cl Se
RI
+ PCl5
N N N+ N
H
R I– R
(88)
Scheme 41
S SMe Se
MeI NaHSe
+ I– (26)
R X R R X R R X R
X = O, S (89)
O Cl Se
R R R R R R
POCl3 K2SeO3
(27)
Me2NCHO
R S R R S R R S R
+
(90)
The resonance!stabilized selone "80# can also be prepared via a similar displacement "Scheme 31#
ð64CC248Ł[ The spectroscopic properties of this molecule\ described as a {{quasi!selenourea\|| indicate
a strong p!conjugation interaction between the amino groups and the selenocarbonyl group through
the cyclopropene ring[
R2N
+ Cl
NaHSe, EtOH, H2O
+
R2N ClO4– R2N R2N R2N
Se + Se– Se–
An anionic resonance!stabilized selone "81# can also be prepared via a displacement sequence
"Equation "17## ð65AG"E#693Ł[
O O Ph Se Ph Se– Ph Se–
H2Se
2+ (28)
pyridine
Ph Br –O O O O –O O–
(92)
Finally\ the preparation of compounds "82# and "83#*formally containing a selone moiety*involves
the thionation of a diselenacyclopentene "Equation "18##\ readily available via ring opening of the
selenopyrone followed by oxidation "cf[ Scheme 28# ð51G748\ 53G37Ł[ These compounds are probably
better envisioned as containing hypervalent selenium and sulfur\ stabilized by {{no!bond resonance||[
399 Seleno! and Telluroaldehydes and !ketones
Se Se O P2S5 Se Se S Se S S
(29)
Se Se S Se S S
(93) (94)
Te
Te
O Te 28%
dioxane
+ (Me2Al)2Te
100 °C
Te
(95) (96)
Scheme 43
The _rst stable tellone\ 0\0\2\2!tetramethylindanetellone "87#\ has been reported in the early 0889s[
This compound can be prepared by thermolysis of the corresponding 0\2\3!telluradiazoline "86#
"Scheme 33# ð82JA6908Ł[ The telluradiazoline "86# was prepared by a telluration sequence involving
the N!telluronitrosoimine "88# as an intermediate "Scheme 34# ð82CL0936Ł[ This sequence is similar
to that described for the preparation of selones "cf[ Scheme 15#[ The intermediate "88# can lose
tellurium to a}ord the diazo compound or extrude nitrogen to a}ord the tellone[ The tellone and
the diazo compound undergo a cycloaddition to a}ord the telluradiazoline[
N N
TeCl2, Et3N 80 °C
NNH2 Te
5 °C, benzene Te
(97) (98)
Scheme 44
A stable metal complex of tellurobenzophenone "099# has been prepared by reaction of the
corresponding metal carbene complex with tellurocyanate "Equation "29## ð72JOM"141#C52Ł[ Similar
Telluroketones 390
R
N2
–Te R
R NH2 R N Te
TeCl2
N N
R R
R Te R
(99) N –N2
Te
R N
R
R R N N
Te + N2 R R
R R R Te R
Scheme 45
to the related selenocarbonyl metal complexes\ these compounds retain tellurocarbonyl character
and react as would be expected for a free tellone ð75JOM"188#C6\ 77JOM"237#C0Ł[
(100)
Finally\ a bridged metal complex of telluroacetone "091# has been prepared by insertion of
dimethyldiazomethane into the tellurium complex "090# "Scheme 35# ð73CC575Ł[
•
Al2Te3, HCl • • –N2
Mn Te N2
OC O Mn Mn
CO OC CO OC CO
(101)
•
OC CO
Mn Te
Mn
OC CO
•
(102)
Scheme 46
Copyright # 1995, Elsevier Ltd. All R ights Reserved Comprehensive Organic Functional Group Transformations
3.10
Imines and Their N-Substituted
Derivatives: NH, NR and
N-Haloimines
GRAEME M. ROBERTSON
Glaxo Research and Development, Stevenage, UK
2[09[0 IMINES 393
2[09[0[0 General Methods for Imine Synthesis 393
2[09[1 N!H IMINES 393
2[09[1[0 N!H Aldimines 393
2[09[1[1 N!H Ketimines 394
2[09[2 N!CARBON!SUBSTITUTED IMINES 394
2[09[2[0 N!Carbon!substituted Aldimines 395
2[09[2[1 N!Carbon!substituted Ketimines 396
2[09[2[1[0 Formation of N!carbon!substituted ketimines via condensation reactions 396
2[09[2[1[1 Formation of N!carbon!substituted ketimines via rearran`ement reactions 396
2[09[2[1[2 Formation of N!carbon!substituted ketimines via oxidation or reduction reactions 396
2[09[2[1[3 Formation of N!carbon!substituted ketimines via miscellaneous methods 397
2[09[2[2 Cyclic Imines 398
2[09[2[3 a\b!Unsaturated Imines 300
2[09[2[3[0 Aryl aldimines 300
2[09[2[3[1 Aryl ketimines 301
2[09[2[3[2 a\b!Unsaturated ketimines 302
2[09[2[3[3 Aza!0\2!dienes 302
2[09[2[4 Chiral Imines 303
2[09[2[5 a! and b!Haloimines 304
2[09[2[6 Acylimines 306
2[09[2[6[0 N!Acylimines 306
2[09[2[6[1 a!Acylimines 306
2[09[2[7 Diimines 306
2[09[2[8 C!Metal Derivatives of Imines 307
2[09[2[09 a!Sulfenylimines 307
2[09[3 N!HALOIMINES 308
2[09[4 IMINIUM ION SALTS 308
2[09[4[0 Iminium Ions 308
2[09[4[0[0 Iminium ion cyclizations 319
2[09[4[1 N!Acyliminium Ions 311
392
393 Imines and NH\ NR and N!Haloimines
2[09[0 IMINES
NHR R R
N [E+] N
–
E
[H] base
R
N
acid
R = chiral auxiliary R = (CH2)nCH=CH2
H R
N HN
( )n
Scheme 1
The literature on the synthesis\ properties\ and chemical reactions of imines "and azaallyl anions#
up to 0868 has been reviewed previously ð68COC"1#274Ł[ Several other reviews are available "in
addition to those that cover enamine or imine anion chemistry# ð52CRV378\ B!69MI 209!90\ 71T0864\
71T2252\ 72S406\ B!72MI 209!90\ 75T4046Ł[ The traditional method for the formation of ketimines by
condensation of a primary amine with a ketone is generally quite straightforward[ In contrast\ the
corresponding preparation of aldimines can be di.cult\ especially with relatively unhindered and
thereby reactive aldehydes\ where further reaction including the formation of aminals can be a
problem[ However\ these aminals often undergo loss of one amine unit thermally "typically during
distillation# to generate the imine ð47JCS1198Ł[
Iminations of aldehydes\ ketones\ and acid chlorides have been achieved using bis"dichloro!
aluminum# phenylimide\ which in turn is prepared from ethylaluminum chloride and aniline
ð75JOC0737Ł[ This oxophilic iminating reagent is especially useful for the selective conversion of a\b!
unsaturated ketones into anils\ with no detectable addition to the C1C linkage[
MgCl NH
R2MgCl, THF, CuBr N NH3 (dry)
R1 CN
∆ R1 R2
R1 R2
Scheme 2
N!H Ketimines have also been prepared by routes not involving carbonyl derivatives[ For
example\ in a related manner to N!H aldimines\ N!H ketimines "R0 or R1 aryl# can be prepared
by the base!catalyzed decomposition of N!alkyloxaziridines "Equation "1## ð75JCS"P0#756Ł[ Alter!
natively\ direct lithiation in the presence of phenanthrene as a hydrogen acceptor\ allows the
preparation of lithiated imines[ Alkylation of the resulting anions then leads to the synthesis of
homologated products ð73S836Ł[
O NH
dabco or ButOK
(2)
N R1 R2
R2
R1
R1
NH R1 R2
+ R2 CO2R3 N CO2R3 (3)
Ph Ph H2N
HCl
Ph Ph
O
R1MgBr, THF, –80 °C to –20 °C
R2 (4)
N R1 N
R2 TMS
N!Substituted aldimines can be prepared via the hydrogenation of imidoyl chlorides using
dichlorobis"triphenylphosphine#palladium in the presence of triethylamine as acid scavenger
"Scheme 2# ð74S856Ł[ This procedure permits the indirect synthesis of N!substituted aldimines
from secondary amides[
O
R2 R2
N H2, PdCl2(PPh3)2 N
H
R1 N
Et3N, C6H6, 120 °C
R2 R1 Cl R1
Scheme 3
Remotely functionalized aldimines can be obtained from the Michael addition of enamino!
stannanes to a\b!unsaturated esters and nitriles "Equation "4## ð79JOM"075#C8Ł[ Iminocyclopropanes
can be prepared by the base!induced cyclization of a!bromoketimines via a 0\2!elimination of HBr
ð79LA0703Ł[
SnBu3 N
R1
N R2
R1 + CO2Me (5)
R2 CO2Me
N!Carbon!Substituted Imines 396
2[09[2[1 N!Carbon!substituted Ketimines
R1
O
R1 Bu2SnCl2, toluene, ∆ R2 N
X
+ (6)
X
R2 NH2
Further\ with dibutyltin dichloride as the catalyst\ the extent of racemization in chiral ketones
occurs is not as marked as with other reagents[
The reaction of ""trimethylsilyl#methyl#iminotrophenylphosphorane\ prepared in situ from "tri!
methylsilyl#methyl azide and triphenylphosphine\ with carbonyl compounds or heterocumulenes\
provides a one!pot synthesis of the corresponding N!""trimethylsilyl#methyl#imines or ""trimethyl!
silyl#methyl#!substituted heterocumulenes respectively\ which are versatile reagents for heterocyclic
synthesis ð73JOC1577Ł[
Ph Ph Ph H
+
PhCH2NEt3 Cl–
N + Ar2 N (7)
Ar1 N Ph N Ar2
Ph Ph Ar1
Primary amines add to triple bonds to give enamines that have a hydrogen on the nitrogen and
tautomerize to the more stable imines ð54RCR558Ł[
Treatment of enamines with a nitrilium salt\ also gives imines ðB!77MI 209!90Ł[
Imines can be prepared from active hydrogen compounds by the treatment with a nitroso
compound ðB!81MI 209!90Ł[
Bis"dichloroaluminum# phenylimide\ prepared from ethylaluminum dichloride and aniline\ is
a highly selective reagent for the formation of N!substituted imines from carbonyl compounds
ð75JOC0737Ł[ It is of particular use for ketimines bearing two or more aromatic groups and for the
transformation of a\b!unsaturated ketones into anils[ Palladium"9#!catalyzed additions of disilanes
to isocyanides provide a convenient method for the preparation of N!substituted bis"silyl#imines
"Equation "7## ð76TL0182Ł via a palladium"9#!mediated insertion of isocyanide into the siliconÐtin
bond[
SiR3
Pd(PPh3)4, toluene, ∆
R3Si SiR3 + R1 NC R3Si N (8)
R1
Tertiary alkyl ketimines can be prepared by the reaction between a tertiary alkyl isocyanide and
t!butyllithium to give a tertiary lithium aldimine "1#[ This lithium imine acts as an acyl anion
equivalent and undergoes alkylation with aryl\ vinyl\ and alkynic halides\ to give the corresponding
imines\ which upon hydrolysis yield the parent ketones "Scheme 3# ð71JOC41Ł[
ButLi, –40 °C
Li
NC RI
But But
N But
(2)
R H3O+ O
But
N But R But
Scheme 4
Imines can be obtained by the palladium!catalyzed reaction of ternary systems comprising bromo!
benzene\ t!butyl isocyanide\ and an organotin compound "Equation "8## ð75CL0086Ł[
N!Carbon!Substituted Imines 398
Pd(PPh3)4 Ph N
PhBr + ButNC + Bu3SnR But (9)
R
Ketimines can be prepared by the reaction of imidoyl chlorides with a variety of organotin
compounds in the presence of a catalytic amount of a palladium complex\ such as dichloro!
bis"triphenylphosphine#palladium at 019>C in xylene ð75BCJ566Ł[
An improved synthesis of trialkylketimines by the reaction of a!cyanoenamines with MeLi has
been published ð71OPP102Ł[
Cyanimides have been obtained by treatment of cyanamides with lead tetraacetate ð75S0944Ł[
Since cyanimides can be hydrolyzed to carbonyl compounds\ the method can also be used to prepare
aldehydes and ketones from primary amines "Scheme 4#[
O NH
i or ii
iv
CN
N
CN Pb(OAc)2 CN
iii
N H N
O O H
Reagents: i, BrCN, Et2O, –30 °C to 25 °C; ii, EtOH, AcOH, NaOCN, ∆; MsCl, pyridine, 0 °C to 25 °C;
iii, c-C6H12, Pb(OAc)4; iv, benzene, Al2O3
Scheme 5
Cl Cl
Scheme 6
Acyl nitronates are readily obtained from ketones and nitroalkenes\ and they serve as useful
intermediates for the synthesis of cyclic imines and amines "Scheme 6# ð89CL128Ł[
R2
H2, 5% Rh on Al2O3, MeOH
R1 + OAc R1 R2
N N
H
O O–
R1 pyridinium p-toluenesulfonate
R2 R2
HO N CHCl3, 60 °C R1 N
H
Scheme 7
Ar
Ar
[Cu(PPh3)Cl]4, THF, ∆
Ar N O N•
N
Ph
Ph
Cu–O Ph
Scheme 8
Cp
Cp
NH2 Ti Cl N
CpTiCl3, MeLi, THF N Ti Cl
N
R
R
R
R
Scheme 9
H
PPh3, THF
Cbz Cbz N
N N3 N N
H 2N
Ph Ph
Scheme 10
Cyclic imines ranging from D0!pyrrolines to 0!aza!0!cycloheptenes can also be prepared via the
boric acid mediated decarboxylation of the corresponding exocyclic b!enaminoester "Equation "00##
ð76TL1242Ł[
R H3BO3, 180 °C
( )n R (11)
N ( )n
EtO2C H N
Cyclic imines\ like their acyclic counterparts ð67JOC0356Ł\ can be generated from the parent amine
via conversion into an N!chloramine precursor with t!butyl hypochlorite\ followed by treatment
with potassium superoxide in ether ð79JOC0404Ł[ The imine can then be used in a subsequent reaction
with organolithium reagents to give alkylated amines regioselectively "Scheme 00#[
( )n ( )n
KO2-crown ether ( )n
ButOCl
N N
H N
Cl
Scheme 11
Speci_c baseÐsolvent combinations that promote kinetic deprotonation can control the orien!
tation of 0\1!eliminations from cyclic imines to give the thermodynamically disfavored isomer
ð68TL1098Ł[ Thus N!chloro!1!ethylpyrrolidine gives substantial proportions of 4!ethyl!0!pyrroline
"2# "Equation "01##[
( )n
( )n ( )n
base
N Et + (12)
N Et Et N
Cl
(3)
NaOMe, MeOH 96:4
ButOK, ButOH 73:27
ButOK, hexane 58:42
ISiCl3, ClCH2CH2Cl
ArCHO + CHO (13)
CN Ar N
Two reports of the N!alkylation of Schi} bases by a\b!unsaturated esters and nitriles have
been published ð68CB0186\ 68TL2342Ł[ a\b!Unsaturated imines are also formed from thiazolidine!3!
carboxylic acid esters upon treatment with Ag1CO2 in aprotic solvents "Equation "03## ð68CB096Ł[
RO2C CO2R
NH Ag2CO3
(14)
N
S Ar
Ar
H
Fremy's salt + Ar NH2 H2N N Ar Ar N Ar
Ar NH2 Ar NH2
5% Na2CO3
Ar (5)
(4)
Scheme 12
S NH•HCl
+ Ar1MgBr (15)
Ar NH2 Ar Ar1
EtMgBr Ph2CO N Ph
Ar
ArNH2 ArN(MgBr)2
Ph
(6)
Scheme 13
Cobalt Schi} base complexes catalyze the selective oxidations of secondary anilines with t!butyl
hydroperoxide to give the corresponding imines ð80CL0982Ł via a single electron transfer "SET#
dehydrogenation mechanism[
Arylimines can be obtained by the addition of N!silylated amides to the corresponding arylÐ
N!Carbon!Substituted Imines 302
lithium compound "Scheme 03# ð75TL496Ł[ Imine formation is strongly dependent on the basicity
of the lithium reagent\ and fails for alkylÐlithium analogues[
O R1 R2
ArLi Ar N
TMS TMS
R1 N LiO N
R2 Ar R1
R2
Scheme 14
O R2 O OAc
R2COCl, C5H5N, THF AcCl, C5H5N, THF
O
R2 = Ph, But
N N N
R1 H R1 Ac R1
(8) (7) (9)
Scheme 15
2[09[2[3[3 Aza!0\2!dienes
The extensive use of azadienes in DielsÐAlder reactions has been reviewed with particular emphasis
on mono! and bisaza systems ð72T1758Ł[
"i# 0!Aza!0\2!butadienes
Advances in the 0879s in the chemistry of imines with an emphasis on 0!aza!0\2!butadienes and
their cycloaddition reactions have been reviewed ð76H"15#666Ł[
The increasing use of azabutadiene systems in synthesis has led to renewed e}orts directed towards
their preparation[ 0!Aza!0\2!dienes can be prepared by the mercury"II# chloride!mediated addition
of amines to 0\2!enynes in basic wet THF "THF ] H1O\ 3 ] 0# ð74CC0264Ł[
303 Imines and NH\ NR and N!Haloimines
"ii# 1!Aza!0\2!butadienes
1!Aza!0\2!butadienes have been widely studied as a result of their importance in DielsÐAlder
reactions ð72T1758\ 74TL36Ł[ Several routes are available for their synthesis including caesium ~uoride!
induced protiodesilylation of N!"0!trimethylsilylallyl#imines ð74TL36Ł[ Unactivated 1!aza!0\2!buta!
dienes\ which can be prepared by an imine dimerization reaction e}ected with TFA in THF
ð74CB2541Ł\ undergo cycloaddition reactions with dialkyl azodicarboxylates and heterocumulenes
ð75CC0068Ł[
1!Aza!0\2!butadienes can be prepared by base!catalyzed isomerization of the corresponding
unconjugated analogues "09# "Scheme 05#\ and have been used in a three!step N!heterocyclic
annulation procedure for the synthesis of 2\3!dihydro!1!quinolines ð72JOC4237Ł based in the thermal
electrocyclization of 0!aryl!1!azabuta!0\2!dienes[
R
R R R
600 °C N
Ar
Ar O Ar N Ar N
(10)
Scheme 16
Ar2
Ar1 N Ph i, NaH–HMPA, THF
N Ph (16)
Ar2CO2
Ph ii, Ar2COCl, THF, 0 °C
Ar1 Ph
Several substituted 0!thia!2!azabutadienes have been prepared and their reactions with ketenes
a}ord 5H!0\2!thiazine!5!ones ð75PS"16#216Ł[
Wittig reactions of N!acrylic phospha!l4!azenes with aldehydes provide a useful entry to 2!ethoxy!
carbonyl 1!aza!0\2!dienes "Equation "06## ð77TL3752Ł[
CO2Et
CO2Et R1
R1 R2CHO, CHCl3, 60 °C
N (17)
N
PPh3
R2
R* R* R*
N N N
H
EWG EWG
Scheme 17
N!Carbon!Substituted Imines 304
The reaction can be highly regio! and stereoselective\ and is a powerful alternative to the Stork
enamine reaction[ For example\ Michael!type alkylations of chiral imines have facilitated the
enantioselective synthesis of molecules containing quarternary centers ð74JA162Ł[ Although generally
used for the synthesis of functionalized ketones\ the process can be arrested at the imine stage to
give similarly functionalized chiral imines[
The other major areas for chiral imines\ is as intermediates for the preparation of chiral amines
and ketones[ For example\ alkylation of the "R#!camphor imine of t!butylglycinate "00# a}ords the
imines "01# for which de|s of 64Ð099) were observed when Rallyl "Equation "07## ð75CJC615Ł[
The greater diasteroselectivities in the cases of allylic imines "with de of about 49)# probably results
from an interaction between the p!systems of the allylating agent and the imine\ so that alkylation
occurs from the pro!R!face\ for steric reasons[
Chiral camphor derived imines have also been used for the enantioselective synthesis of "R#!a!
substituted primary benzyl amines\ via alkylation of the 09!substituted "¦#!camphor derivative "02#
ð89SC04Ł[
H
N Ph
N
O
OH
(13)
Asymmetric syntheses of both "R#! and "S#!a!substituted benzylamines\ are possible via the
alkylation of chiral pinanone ketimines "Scheme 07# ð78SC0312Ł[ An important feature of this
procedure is that the diastereoselectivity of the alkylation is independent of the alkylating agent
used[
RX, –78 °C *
R
H2N
*
R
Scheme 18
Some examples of work in the preparation of chiral ketones include] "i# the use of chiral imines
prepared from cyclohexane and methoxyamines derived from D!camphor derivatives which readily
undergo metallation and alkylation to give 1!alkylcyclohexanones of high enantiomeric purities
ð75CPB0949Ł\ and "ii# ~uoroacetone imines of cyclohexylamines which undergo regioselective depro!
tonation with BunLi\ followed by stereoselective alkylation "Scheme 08# ð77JOC1880Ł and subsequent
hydrolysis to give 1!~uoro!1!alkylcyclohexanones[
Scheme 19
in particular in the synthesis of cyclopropanimines\ have also been surveyed ðB!77MI 209!91Ł[ Other\
more speci_c\ reviews covering their synthesis ð68OPP004Ł and reactivity ð79OPP38Ł are also available[
There are two main strategies for the synthesis of a!haloimines[ The _rst strategy was the
condensation of an a!halogenated carbonyl compound with a primary amine under suitable reaction
conditions\ similar to the usual synthesis of imines from carbonyl compounds and primary amines[
The second approach involves the halogenation of imines[ The _rst method gives rise to a!haloimines
only in special cases[ A range of side reactions is commonly encountered\ including] nucleophilic
a!substitution\ elimination of hydrogen halide\ haloform!type reactions\ Favorskii rearrangements
ð75JOC2728Ł\ and rearrangements via intermediate epoxides[ In many cases the initially formed
a!haloimino compounds undergo further transformations under the given reaction conditions[ Thus
cyclopropylidene amines can be isolated from the treatment of a!haloimines with base under
Favorskii!type conditions ð79LA0703\ 75JOC2728Ł[
The second approach to a!haloimines\ via halogenation of imines\ can also be problematical\
owing to formation of unstable immonium!type compounds during these reactions prior to aqueous
workup[ Aldimimes are selectively a!monochlorinated by a sequence of reactions involving
a!trimethylsilylation of preformed 0!azaenolates\ a!chlorination using NCS\ and desilylation in
MeOH ð80CC637Ł[ a!Chloroketimines can be prepared from ketones via simple chlorination ð71S32Ł\
and they undergo facile conversions into cyclopropylimines upon treatment with base "Scheme 19#
ð77CC714Ł[
R2 R2
O i, chlorination
N LDA, THF, 0 °C
N
NaOMe, MeOH
R1 R1 R1
ii, R2NH2, TiCl4 R3X
R3
Cl Cl
R2 H R2
N R2HN OMe N
LiAlH4, Et2O
R1
R1 R1
R3
R3 R3
Scheme 20
2[09[2[6[0 N!Acylimines
N!Acylations of alkylimidate hydrochlorides to a}ord alkyl N!acylimidates\ have been
accomplished with triethylamine ð74CB2978Ł[ N!Acylimines can be prepared from methyl trichloro!
pyruvate\ by reaction with amides\ followed by chlorination and treatment of the resulting
a!chloroacylamine with triethylamine ð74S066Ł[ The utilization of N!acylimines and especially
N!acyl and N!thioacylimines\ as the heterodiene in ð3¦1Łcycloaddition reactions has been reviewed
ð78CR0414Ł[
2[09[2[6[1 a!Acylimines
a!Bromo esters and ketones can both be converted into their respective a!acylimines[ Thus
conversion of a!bromo esters to the corresponding azide\ and treatment with lithium ethoxide in
ethanol gives a quantitative yield of the target a!imino ester o}ering an improved method for the
preparation of such compounds "Scheme 10# ð79JOC3841Ł[
Br N3 NH
OEt NaN3, DMF OEt LiOEt OEt
R R R
O O O
Scheme 21
Ph TMS Ph
N O N O
KF, crown ether
R3 + (19)
R1 R4 Cl R1 R4
R2 R2 R3
a!Iminonitriles\ which are useful as intermediates for heterocyclic synthesis\ have classically been
prepared from nitrones and sodium or potassium cyanide ð67S781Ł[ Improved yields of b!ketimines
can be obtained by the alternative reaction of aldonitrones with cyanotrimethylsilane in the presence
of Et2N ð74SC224Ł[
Reactions of phenyl glyoxal with primary amines have allowed the synthesis of some monoimines
ð73JCR"S#033Ł[
a!Ketodicarboxylic acid chloride imine chlorides\ which readily undergo cyclization to N!hetero!
cycles\ can be prepared by a!addition of dicarboxylic acid chlorides to isocyanides "Equation "19##
ð75LA021Ł[
O
(COCl)2 O NR
R NC (20)
Cl Cl
2[09[2[7 Diimines
0\1!Diimines "together with a!iminoketones and a!aminopropionamidines# can be prepared by
oxidative alkyl and arylaminomercurations of prop!1!ynyl alcohols ð72JCS"P0#0982Ł[
0\1! and 0\2!Diimines can be prepared directly from the corresponding dicarbonyl compounds
307 Imines and NH\ NR and N!Haloimines
via titanium tetrachloride!catalyzed condensation reactions with the appropriate amine "Scheme
11# ð76OPP070Ł[
R3
O N
R2 R3NH2, C6H6, TiCl4, 25 °C
R2
R1 R1
O N
R3
O O R3 R3
R3NH2, C6H6, TiCl4, 25 °C N N
R1 R2
R1 R2
Scheme 22
The preparations and reactions of mono! and diimines of quinones have been reviewed ðB!69MI
209!93Ł[
In principle\ the condensation reaction of 0\1!diones with amines should be a straightforward
reaction\ but condensations with branched amines can be problematical[ However\ branched amines
with secondary or tertiary a!carbons can be condensed with glyoxal to give chiral 0\1!diimines
"diazadienes# by using formic acid as a catalyst and an excess of a drying agent in a nonpolar solvent
ð73CB583Ł[
Symmetrical 0\3!diimines can be prepared by dehydrodimerization of a!bromoimines using LDA
ð75TL0696Ł via a single electron transfer reaction[
2[09[2[09 a!Sulfenylimines
a!Sulfenylations of simple imines can be achieved via nucleophilic substitution of their a!halo
counterparts with the desired sodium thiolate in re~uxing methanol\ or by the condensation of
a!"alkylthio#aldehydes with a primary amine "Scheme 12# ð72S521Ł[
Scheme 23
R
Br2, CsF
R CN F N (21)
Br
O O
H H
Ph N Ph N
TFA, CH2Cl2 +
BocHN H N (22)
O N CF3CO2– N
Z Z
(14)
Intramolecular 0\2!dipolar cycloaddition of azides with v!chloroalkenes gives the thermally labile
triazolines "04#[ In situ rearrangement and intramolecular N!alkylation then gives the bicyclic 0!
pyrroline iminium ion "05# "Scheme 13# ð89TL6460Ł[
Imination of N!alkyl pyridinium and quinolinium salts can be achieved via oxidation of the
appropriate substrates with potassium permanganate in liquid ammonia ð73TL2652Ł[ Quinone imin!
ium dyes are of particular use in copying and other printing processes and can be prepared
straightforwardly from aromatic amines using DMSO as the methylating agent\ with a Lewis acid
such as TiCl3 as a catalyst ð75T3406Ł[
2!"a!Dialkylaminoarylidene#!0!alkylthiotriazenes\ which are readily obtained from thioamide
salts\ a}ord diamidinium iodides when treated with methyl iodide "Equation "12## ð75JCS"P0#508Ł[
319 Imines and NH\ NR and N!Haloimines
Cl
O O Cl
O C6H6, ∆
O N
N N
N3
(15)
O OH
O H
ii, ButNH2, KHMDS
O O
iii, BH3•THF, NaOAc, MeOH, H2O2
N N
Cl– +
(16)
Scheme 24
+
NR22 MeI, Me2CO R22N N NR22
(23)
N SMe
R1 N N R1 R1
The photochemistry of iminium salts and related heteroaromatic systems has been reviewed
ð72T2734Ł[ The SET!induced photospirocyclizations of allylsilane!terminated iminium ions\ such as
"06#\ have been utilized by Mariano and his co!workers as a versatile route to spirocyclic amines
including the harringtonine alkaloids "Scheme 14# ð78TL3074Ł[
Ar
ButCO2 Ph O
+
Ph Ar N
N hν, MeCN, NaHCO3 ButCO2 N O
ButCO2
TMS
(17)
Scheme 25
NC
N H OH
TMS
OBn
(18)
Iminium Ion Salts 310
An elegant and focused method for iminium ion cyclizations of this type is the antarafacial
addition of an internal iminium ion and an external nucleophile to an alkyne\ via an intermediate
delocalized cation "08# "Scheme 15# ð77TL890Ł[ This method of nucleophile promoted iminium ion
cyclization allows the facile conversion of amines into cyclic amines with a b!exocyclic double bond
of de_ned geometry ð77JA501Ł[ Iminium ion vinyl silane cyclizations can also be induced with Lewis
acid catalysts such as TiCl3 as in the synthesis of the piperidine "19# "Scheme 16# ð89JOC0975Ł[
Reverse addition of the a!aminonitrile to TiCl3 in CH1Cl1 is critical to achieve a successful cyclization[
+
CSA, (HCHO)n, NaI, H2O, 100 °C
NH N
H
H
OH OH
(19)
Scheme 26
R
TMS CN R
TiCl4, CH2Cl2 Pd/C, H2, MeOH
N N
R NH
Ph Ph
(20)
Scheme 27
Iminium ions can be conveniently generated from a!methoxy amines in a Lewis acid catalyzed
procedure[ The required a!methoxy amines are readily generated electrochemically via the oxidation
of the parent amine to provide a chemoselective entry to functionalized substrates for iminium ion
cyclization ð82JA0323Ł[ This method has been utilized in a synthesis of the angiotensin!converting
enzyme inhibitors "−#!A47254A and "2#!A47254B "Scheme 17#[
OH OMe
O O O O O
O
i, Anodic oxidation
N OH N OMe ii, TiCl4
( )n ( )n
OH Cl
OMe
O O O
N OMe
( )n
Scheme 28
311 Imines and NH\ NR and N!Haloimines
The in situ generation of iminium ions for use in tandem reaction sequences\ such as the cationic
aza!Cope "1!azonia!ð2\2Ł!sigmatropic# rearrangement of iminium salts "Scheme 18# was _rst reported
in a ring expansionÐpyrrolidine annulation reaction of cyclopentane!derived amino alcohols
ð72JOC2282Ł[ This tandem cationic aza!Cope rearrangementÐMannich cyclization procedure has
since been applied to the synthesis of a range of alkaloids\ including Aspidosperma ð72JOC1574Ł\
Melodinus ð78JOC0125Ł\ and Amaryllidaceae ð78TL536Ł alkaloids[
Ar Ar Ar O
HO HO HO Ar
R2CHO, H+
+ +
R2
H
N N R2 N R2 N
R1 R1 R1 R1
Scheme 29
MeO
MeO Br
H2NCH(Ph)CH2OH + Et3N, CH2Cl2, –78 °C
N Ph
MeO
AcOH, EtOH
MeO CHO Br–
HO
MeO MeO
i, MeMgI, THF, Et2O, –78 °C
N NH
MeO Ph ii, H2, Pd/C, acidic EtOH MeO
O
(21)
Scheme 30
TMS
O
O
+
N
N H
BF3•OEt2, CH2Cl2
N OR
N H OR
Ac
Ac
N
H
CO2Me
Scheme 31
R1 Ph H
R1 OR4 +
+ R43O+ SbCl6– N TFA N
N
O O
R2 CF3SO3–
R2 R3
R3 R
(22) (23)
Scheme 32
Copyright # 1995, Elsevier Ltd. All R ights Reserved Comprehensive Organic Functional Group Transformations
3.11
Imines and their N-Substituted
Derivatives: Oximes and their
O-R Substituted Analogues
GRAEME M. ROBERTSON
Glaxo Research and Development, Stevenage, UK
2[00[0 OXIMES AND THEIR DERIVATIVES 314
2[00[0[0 Oximes of Aldehydes and Ketones 314
2[00[0[0[0 Preparations of oximes from carbonyl compounds 314
2[00[0[0[1 Preparations of oximes from noncarbonyl compounds 315
2[00[0[0[2 Miscellaneous methods for the preparation of oximes 316
2[00[0[0[3 a\b!Unsaturated oximes 318
2[00[0[0[4 Cyclic oximes 329
2[00[0[1 O!Carbon!substituted Oximes 329
2[00[0[2 Nitrones and Related Derivatives 320
2[00[0[2[0 Acyclic nitrones 320
2[00[0[2[1 Cyclic nitrones 323
2[00[0[2[2 Miscellaneous nitrone derivatives 324
2[00[0[3 O!Chalco`en!substituted Oximes 324
2[00[0[4 O!Arsenic!substituted Oximes 324
2[00[0[5 O!Silicon!substituted Oximes 325
2[00[1 N!HETEROATOM ANALOGUES OF OXIMES 325
2[00[1[0 Sulfur Analo`ues 325
2[00[1[0[0 Sulfenimines 325
2[00[1[0[1 Sul_nimines 326
2[00[1[0[2 Sulfonimines 326
2[00[1[1 Phosphorus Analo`ues 328
2[00[1[2 Nitro`en Analo`ues 328
2[00[1[3 N!Silicon!substituted Imines 328
314
315 Oximes and their O!R Substituted Analo`ues
ðB!61MI 200!90Ł[ Derivatives of hydroxylamine\ e[g[\ NH1OSO2H and HON"SO2Na#1\ have also been
used[
For hindered ketones\ such as hexamethylacetone\ high pressures ð48JA1040Ł or prolonged reaction
times may be necessary[ It has also been shown ð48JA362\ 53MI 200!90Ł that the rates of formation of
oximes are at a maximum when the acidity of the mixture is about pH3[
Ketones can also be converted into their oximes by a trans!oximation reaction[ Other oximes
such as ethyl a!"isopropylidene#aminooxylpropionate ð54JOC0296\ 62OSC"4#0920Ł\ and aldehydes or
ketones can be converted into oximes using acetone oxime in acetic acid ð78JPR769Ł[
NO2 OH
KH, (TMS)2S, THF, ∆ N
R1 (1)
R2 R1
R2
Oximes 316
Methods available for the direct conversion of aliphatic nitro compounds into oximes in the
presence of acid!sensitive groups\ or other reducible functionalities\ are relatively rare[ The best
conditions for such systems is reduction in carbon disul_de\ in the presence of triethylamine
ð76T440\ 89S222Ł[ Alternatively\ nitro compounds can be converted into oximes photochemically by
irradiation in acetone in the presence of Et2N "Equation "1## ð78S195Ł[ a!Nitroketones can also be
converted into the corresponding oxime\ by irradiation in 1!propanol ð62BCJ2087Ł[ Primary aliphatic
amines that lack an a!hydrogen can be oxidized to oximes under acidic conditions\ via an inter!
mediate nitroso compound ð59CB021Ł[
NO2 OH
hν, Et3N, acetone N
(2)
R1 R2 R1 R2
Homologated oximes can be obtained in good yields from nitro compounds after activation
with N\N!dimethylchloromethyleniminium chloride followed by treatment with a Grignard reagent
"Scheme 0# ð72CL0426Ł[ Alternatively\ homologated ketoximes can be prepared via carbonÐcarbon
bond formation by regioselective attack of Grignard reagents at the a!position of aci!nitro com!
pounds activated by Vilsmeier|s salt in the presence of copper"I# iodide as a catalyst ð72CL0426Ł[
Since aci!nitro compounds are available by the treatment of nitro compounds with n!butyllithium\
this method provides an indirect route for the conversion of nitro compounds into homologated
ketoximes[
BuLi, THF
+ O– DMF, (COCl)2, CH2Cl2
R1 N
R1 NO2
O– Li+
R2
Me CuI, R2MgX, THF
+
O N Cl– R1 N
R1 N Me
OH
Scheme 1
O OH
Co(eobe)2, PhSiH3, BuONO, THF O N
(3)
R R
The synthesis of aldohydroximino lactones via oxidations of sugar oximes have been reported
ð74HCA1143Ł[ The oxidations were e}ected by manganese dioxide\ or by mercury"II# acetate and
oxygen in the presence of cuprous chlorideÐpyridine[
Oximes have been generated by electrocyclic ring!opening reactions involving four!membered
cyclic nitrones "N!hydroxy!0\1!dihydroazetes# following treatment with potassium t!butoxide
"Scheme 1# ð75RTC092Ł[
R1 + O– R1 O–
N KOBut N NH4Cl (aq.)
+
CONEt2 CONEt2 K
R2 R2
R3 R3
R1 NOH R1 NOH
CONEt2 + R3
R2 R2
R3 CONEt2
Scheme 2
In the steroid series\ 5!nitro!alkene derivatives have been shown to undergo facile reactions with
ammonia\ methanol\ and zinc to a}ord exclusively the oximes of the corresponding 5!keto!steroids
ð73IJC"B#790Ł[
Cyclic ketones can be cleaved by treatment with NOCl and an alcohol in liquid SO1 to give
v!oximinocarboxylic acids "Equation "3## ð48JA4140Ł[
O CO2Et
NOCl, EtOH, SO2
(4)
N HCl
OH
C!Alkylations or arylations of aldoximes have not been widely reported[ The only examples of
both alkylation ð75S352Ł and arylation ð43JCS0186Ł involve homolytic reaction of free C!radicals[
Thus aldoximes are C!arylated e.ciently by decomposition of arenediazonium salts ð75S352Ł\ and
aldoximes are converted into ketoximes using a mixture of a peroxy ester and a cycloalkane or ether
as the C!alkylating agent ð75S352Ł[ Monosubstituted ketene O!alkyl!O?!silylacetals\ unlike their
disubstituted analogues\ react with nitric oxide or isoamyl nitrite in the presence of TiCl3\ to give
a!ketoxime esters "Equation "4## ð77S794Ł[ This method permits the introduction of a nitrogen
substituent at the a!carbon of the parent carboxylic ester[ a!Ketoxime esters can also be prepared
from electron!de_cient nitroalkenes via formation of cyclic nitronic esters intermediates followed
by their fragmentation by a catalytic amount of base "Equation "5## ð77BCJ350Ł[
O OH
R1 R2 C5H11ONO, TiCl4, CH2Cl2 N
(5)
O-TMS R1 CO2R2
Ar Ar
R1 CO2Me NaOMe, THF R1 CO2Me
(6)
+
N N
R2O O O– OH
Oximes 318
Nitronate salts "RCHNO1Na# act as precursors of hydroxynitrilium ion equivalents\ and react
with aromatic compounds under acidic conditions to give the corresponding oximes via protonated
nitronic acids ð78TL4652Ł[
The a!methyl groups of oximes can be functionalized regiospeci_cally via a cyclopalladation
reaction with sodium tetrachloropalladate to form the dimeric organopalladium species "0# ð74CC015\
74T588Ł[ A variety of b!functionalized products can then be prepared via subsequent func!
tionalization of the C0H bond "Scheme 2#[ For 1!disubstituted cyclohexanone oximes\ A"0\1# strain
dominates and subsequent reactions lead to the selective functionalization of the smaller 1!substituent[
HO Cl Cl
N HO HO
Na2PdCl4, NaOAc, EtOH N Pd PPh3 N Pd PPh3
R1
R3 R1 R1
R2 R2 R3 R2 R3
2
(1)
i, Ac2O, pyridine
ii, Pb(OAc)4
iii, NaBH4
pyridine
HO Cl HO
N Cl HO N OAc
i, Cl2, CCl4 N Pd py i, Pb(OAc)4, AcOH
R1 ii, NaCNBH3 R1 ii, NaBH4, 1M NaOH R1
R2 R3 R3 R2 R3
R2
Scheme 3
The initial product of the addition of NOCl to alkenes is a b!chloro nitroso compound\ and\ if
the carbon bearing the nitroso group also has a hydrogen atom\ isomerization occurs to give a!halo
oximes ð57RCR432Ł[
Procedures for the synthesis of 0\2!dioximes have been reviewed ð80OPP482Ł[
OH
N
EtONO, ClCo(DH2)py, Et4NBH4, C6H6
R (7)
R
CCl3 OH
NH2OH, py, ∆ N
(8)
Scheme 4
O Cl
N Cl HO
Me3Al, n-C6H14, –80 °C N Me3Al, n-C6H14, –80 °C
H2O H2O N
OH
(2)
Scheme 5
Scheme 6
Oximes can be prepared directly from carbonyl compounds via a Peterson!type reaction with the
bissilyl derivative "2# ð76S720Ł\ proceeding via an intermediate adduct which can be quenched
directly to the parent oxime\ or trapped with a range of electrophiles to give O!substituted oxime
derivatives "Scheme 6#[
O O– K+ OE
TMS-(TMS-O)N– K+ (3), THF, –78 °C to 25 °C N ECl, –78 °C N
R1 R2 R2 R1 R2
R1
Scheme 7
Scheme 8
Both these methods are controlled by the availability of the appropriate hydroxylamine[ An
alternative general synthesis of nitrones from aldimines and ketimines is their reaction with the
hydroxylamine derivative\ MeNHOSO2H[ This method has been employed in a convenient prep!
aration of ~uorenone methylnitrone\ a previously di.cult compound to prepare "Equation "00##
ð68OPP84Ł[
NPh Me + O–
N
MeNHOSO3H, MeOH, 0 °C
(11)
Nitrones have been obtained from secondary amines in one step by sodium tungstate catalyzed
oxidation with hydrogen peroxide ð73CC763\ 73H"10#372Ł\ or by oxidation with hydrogen peroxide in
the presence of selenium dioxide as catalyst ð76TL1272Ł[ The latter method is also suitable for the
preparation of nitrones in the presence of alkenes[ Imines can be converted into nitrones by treatment
with potassium permanganate under phase!transfer conditions\ via a ð2¦1Ł cycloaddition type
reaction "Equation "01## ð78JOC015Ł[
R3
R3 KMnO4, CH2Cl2, H2O, pH 4.1
+ R2 (12)
R2 R1 N
R1 N Bu4NCl, NaHSO3, H2O
O–
Nitrones are also available via the electrochemical oxidation of N!hydroxy secondary amines
using a supporting electrolyte such as sodium iodide ð75JOC438Ł[
Ene!type reactions of alkenes ð68T036Ł or allenes ð68RTC07Ł with a!chloronitroso compounds
lead to the formation of N!a!chloroalkyl!N!alkenylhydroxylamine intermediates[ Rearrangement
then provides access to aliphatic ketonitrones\ in excellent yields[
An investigation of the reaction of a!chloronitrosoadamantane with Grignard reagents has shown
that adamantylidene nitrones "4# are formed in yields that vary widely with the nature of the
Grignard reagent "Equation "02## ð79RTC135Ł[ With MeMgX and PhMgX\ the N!methyl! and
N!phenylnitrones can be obtained in 48) and 76) yield\ respectively\ but with all other Grignard
reagents nitrone yields are much lower[ Similarly\ methyl and phenyl Grignard reagents react with
simple a!chloronitroso compounds to give the expected nitrones "5# "Equation "03## ð79RTC167Ł[
NO O–
RMgX N+
Cl R (13)
(5)
R1
Cl NO R3MgX
+ O– (14)
R1 R2 R2 N
R3
(6)
Oximes 322
The reaction between N!chlorosuccinimide and benzil "E#!monooxime\ in the presence of dimethyl
sul_de and Et2N\ a}ords a 3 ] 0 mixture of "E#! and "Z#!isomers of C!benzoyl!C!phenyl!N!methyl!
thiomethylnitrone ð79JCR"S#255Ł[ These methylthiomethylnitrones undergo cyclization under ther!
mal or photochemical stimulation\ leading to oxazoles[
C!t!Butyl!N!phenylnitrone has been prepared\ and its chemistry has been investigated in some
detail ð79JCR"S#011Ł[
Functionally modi_ed cyclic nitrones appear to o}er synthetic potential[ However\ the fact that
such nitrones have not been so utilized re~ects the problems associated with their preparation[
Nitrones of type "6# have now been prepared in high yield\ and their 0\2!dipolar cycloaddition
reactions investigated "Scheme 8# ð79JA262Ł[
N N N N+
Et Et OH O–
(7)
Scheme 9
(8)
N!Alkylations of oximes by alkyl halides or sulfonates yield nitrones ðB!77MI 200!90Ł[ Nitrones
have also been obtained by alkylation of O!trimethylsilyloximes with either trialkyloxonium tetra!
~uoroborates or alkyl tri~ates in dichloromethane solution ð74TL3220Ł[ The same research group
also prepared medium!ring cyclic nitrones by heterolytic fragmentation reactions of bicyclic
g!N!hydroxylaminosulfonates[ This procedure enabled the conversions of decahydroquinolines to
perhydroazulenes to be performed ð74JOC2827Ł[
N!Methylnitrones have been generated in excellent yields by reacting carbonyl compounds with
N!methyl!N\O!bis"trimethylsilyl#hydroxylamine ð74JOC4802Ł\ and a!aroyl!N!phenylnitrones have
been obtained upon oxidation of the adducts derived from silyl enol ethers and nitrosobenzene with
silver oxide ð74S168Ł[
The addition of 1!methyl!1!nitropropane and activated zinc dust to a cold ethanolic solution of
a p!substituted benzaldehyde a}ords derivatives of phenyl!t!butylnitrone in high yields ð74JOC0420Ł[
A nitrone derived from an N!hydroxytryptophan ester and methyl ortho!formate provides a route
to b!carbolines via nitrone cycloadditions ð75JOC298Ł[
Sterically unhindered and certain moderately hindered a!chloronitroso compounds "8# react with
trimethylaluminum to give methyl nitrones "09# "Scheme 09# ð75RTC11Ł[
O Me O Me + O–
N Me3Al, n-C6H14, –80 °C N AlMe2 H2O N
R Cl R Cl R R
R R
(9) (10)
Scheme 10
As part of a mild\ multistep procedure for the oxidative deamination of benzylamines\ 3\5!
diphenylpyridinium!1!carboxylates have been converted into nitrones by reaction with p!nitroso!
N\N!dimethylaniline in re~uxing dichloromethane "Equation "04## ð72MI 200!90Ł[
323 Oximes and their O!R Substituted Analo`ues
Ph
NMe2
p-Me2NC6H4NO –O +
N (15)
Ph N CO2 –
+
Ar
Ar
Me
N+ + Me
RCHO, THF, ∆ R N
O– (16)
O–
(11)
O R3
O
R3OTf, CH2Cl2 Et3N, MeCN
OH
R1 N + R2
R1 N –OTf
R2
OH
R3 Nuc
O
NucH, Et3N, MeCN + R2
+ R2 R1 N
R1 N
O–
O–
Scheme 11
1!Butenylmagnesium chloride undergoes 0\1!addition to both aryl and alkyl nitro compounds to
give\ after workup\ the corresponding "E#!nitrone "Equation "06## ð89JOC3345Ł[
R4 R4
N –O CONR42
R1 NO2 +
+ N R3
(19)
R2 R2
R1
R3
OAc O
NO2 O LDA, Ac2O, THF, –78 °C +
+ N
R1 –O R2 (20)
R2
R1
S R2
O S
R1NHOH (aq.) R2I, Me2CO NaHCO3
OH +
Ph N OH
Ph S CO2H Ph N
R1 I–
R1
R2
S
+ O–
Ph N
R1
Scheme 12
R2 R2 R2
TMS-OTf, Et3N
R3 R3 N
R1 R1 R1 O-TMS
NO2 N(O-TMS)2 R3
Scheme 13
2[00[1[0[0 Sulfenimines
The preparations of sulfenimines "also known as sulfenylimines and N!alkylidenesulfenamides#\
together with their structural characteristics\ their reactions\ and the methods for their conversion
into sul_nimines have been reviewed previously\ and the interested reader is directed to these
comprehensive articles ð75JOC4913\ 78CR578\ B!89MI 200!90Ł[
Unlike imines and oximes\ sulfenimines undergo relatively facile stereomutation\ but examples of
stereoisomers of sulfenimines are limited to constrained analogues ð78CR578Ł[ Sulfenimines are
available from sulfenamides by three main routes\ namely] "i# via condensation reactions with
carbonyl compounds^ "ii# from disul_des via reactions with metal salts and carbonyl compounds\
and "iii# via the condensation reactions between sulfenyl halides and imines ð78CR578\ B!89MI 200!90Ł[
They can also be prepared directly from the corresponding sulfenamide\ by treatment with
N!chlorosuccinimide and Et2N ð83SL056Ł[ Application to glycine provides an electrophilic glycine
equivalent for amino acid synthesis[
Sulfenimines are versatile synthetic intermediates\ and undergo nucleophilic additions at the
iminyl carbon\ electrophilic additions at the nitrogen centre\ and alkylation reactions at sulfur
ð78CR578\ B!89MI 200!90Ł[ They have also been reduced to N!sulfur!substituted amines by treatment
with NaBH2CN in TFA ð72JOC2420Ł[ Sulfenimines undergo oxidation to both sul_nimines "sul_nyl
imines# and sulfonimines "sulfonyl imines# "see Sections 2[00[0[1 and 2[00[1[0[2#[
The focus in the 0889s has been on the preparation of chiral sulfenimines ð83MI 200!90Ł and their
utilization as electrophilic glycine equivalents in the synthesis of amino acids "Scheme 03# ð83SL056Ł[
R CO2But
Scheme 14
N!Heteroatom Analo`ues 326
2[00[1[0[1 Sul_nimines
Sul_nimines are more reactive than their sulfenyl analogues\ and they act as ammonia imine
synthons[ Thus\ reduction of the C1N bond with either LAH or NaBH3 a}ords the corresponding
sul_namides\ which readily undergo cleavage at the S0N bond with TFA to give the parent amino
compound ð78CR578\ B!89MI 200!90Ł[ Alternatively\ the intermediate sul_namide can be oxidized to
the corresponding sulfonamide ð71JCS"P0#228Ł[ Chiral sul_nimines are therefore valuable as chiral
ammonia imine synthons in the synthesis of nonracemic amines ð71JCS"P0#228Ł[ They are also
valuable in the synthesis of a!\ b!\ or g!amino acid derivatives\ via either reaction with diethyl!
aluminum cyanide to form a!amino nitriles\ which are readily hydrolyzed to the corresponding
amino acids ð80JOC3\ 83TL8240Ł\ or reaction of nitriles with an alkyllithium followed by reaction
with "−#!L!menthyl "S#!p!tolylsul_nate ð80JOC3Ł[ They also undergo Darzen|s!type reactions with
lithium enolates to form cis!aziridine!1!carboxylic acids ð83JOC2132Ł[
Sul_nimines are generally accessed by asymmetric oxidations of the corresponding sulfenimines
with reagents such as chiral N!sulfonyloxaziridines ð81JOC5276\ 82PAC522Ł\ or by Andersen!type
procedures from metalloimines and menthyl p!tolyl sul_nate "Scheme 04# ð82TL5118Ł\ although this
procedure is limited to the formation of alkyl aryl sul_nimines[
: O
S
p-Tolyl O
dibal MeLi –
R CN AlBui2 AlBui2 Li+
R N R N
:
O
S
p-Tolyl N R
Scheme 15
2[00[1[0[2 Sulfonimines
As with most N!heteroatom!substituted oxime derivatives\ sulfonimines are known by a range of
titles such as sulfonyl imines or oxime sulfonates[ They are highly versatile and reactive reagents
and are readily available from oximes by reaction with sulfonyl halides in the presence of base
ð64S491Ł[ An alternative and general procedure for the preparation of sulfonimines\ even in systems
prone to tautomerization\ is the treatment of carbonyl compounds with sulfonyl chlorides in the
presence of tertiary amines\ such as Et2N ð81JOC3666Ł[ Sulfonimine formation results from a reaction
cascade of amine!catalyzed rearrangement of the initial sulfonyl chloride to a sul_nyl cyanate\
followed by oxime O!sul_nylate formation and subsequent homolytic rearrangement to the sul!
fonimine[
Sulfonimines have proved to be highly useful precursors ð81BSB270Ł[ In particular\ they readily
undergo Beckmann!type rearrangements under a variety of conditions to give a number of
compounds\ e[g[\ in the presence of dialkylaluminum thiolates or selenoates to give iminothioethers
"valuable as activated amide surrogates# and iminoselenoethers\ respectively ð72JA1720Ł[ A similar
reaction with cyanotrimethylsilane and diethylaluminum chloride has a}orded iminonitriles and a!
alkylated amines are available via organoaluminum!promoted Beckmann rearrangement of sul!
fonimines ð72JA1720Ł[ Rearrangement in the presence of TMS!I or Et1AlI gives imidoyl iodides
ð72TL2144Ł[ Regio! and chemospeci_c carbonÐcarbon bond formation results from the Lewis acid
promoted reaction of sulfonimines with silyl enol ethers and provides an e.cient method for the
synthesis of enaminones\ which are useful building blocks for the synthesis of fused carbocycles and
polyheterocycles\ in addition to their reduction to functionalized amino alcohols ð72JA5201Ł[
Alkenic cyclizations promoted by Beckmann rearrangement of sulfonimines provide access to a
range of ring systems\ via four distinct cyclization modes "Scheme 05#\ controlled by the Lewis acid
employed as the initiator and the migratory aptitude of the rearranged group ð72JA561\ 72TL832Ł[
Natural product applications of these reactions have included syntheses of solenopsin B and
327 Oximes and their O!R Substituted Analo`ues
muscopyridine ð72JA561Ł[ Beckmann rearrangement of sulfonimines by reaction with Grignard
reagents gives functionalized imines\ which upon reduction give a!alkylamines ð71TL2284Ł[
endo(B)–endo mode
R
R N
N H
OMs
R2
R2
endo(B)–exo mode
R1 R1 R1
R1 N
N
OMs
( )n
exo(B)–endo mode ( )n
Ph
N NHPh
MsO
exo–exo mode
R
N R
N
MsO
Scheme 16
The C1N bond of sulfonimines is readily reduced under mild conditions with NaBH3
ð70JCS"P0#1332Ł or LAH ð76S608Ł to give the corresponding sulfonamide[ N!Aryl sulfonimines were
used as dienophiles in some of the earliest examples of heterocycle formation via imino DielsÐAlder
reactions ðB!56MI 200!90Ł[ Sulfonimines can also be generated in situ for use in both inter! and
intramolecular DielsÐAlder reactions by treatment of an aldehyde and 0\2!diene with N!sul_nyl!p!
tolylsulfonamide and BF2 = Et1O ð89JOC2926Ł[
Sulfonimines are e.cient acceptors and they readily undergo nucleophilic reactions with organo!
metallic reagents ð72S443\ 73TL4840\ 76TL4004Ł to give a!functionalized N!arylsulfonamides[ Hitherto
the reaction has been of little use for amine synthesis however\ due to the problems of removal of
the sulfonyl group[ This problem has now been overcome by the use of diarylsulfamylimines as the
masked amine functionality\ as these groups are readily hydrolyzed in re~uxing aqueous pyridine
"Scheme 06# ð75TL2846Ł[
R O O R R
O O RM i, pyridine, H2O
S S
Ar N N Ar Ar N N Ar ii, NaOH Ar NH2
H H
Scheme 17
In situ generation of the sulfonimine has also been used for the generation of aldehyde derived
sulfonimine examples\ thus treatment with N!sul_nylsulfonamides a}ords sulfonimines which react
with Grignard reagents to give N!sulfonylamines ð89JOC282Ł[
N!Tosylimines have been synthesized in variable yields by a diisobutyl telluride:copper powder!
induced reaction of aldehydes with tosylazide ð74CL568Ł which does not react even under forcing
conditions[ An organotellurilimine has been proposed as an intermediate "Scheme 07#[
N!Heteroatom Analo`ues 328
Ts
R1CHO R2Te+ N –R2TeO R1
TsN3 + R2Te R2Te NTs
–O NTs
R1
Scheme 18
Ar Ar Ar
R2PCl [O]
O
ArCHO N N N
OH P(O)R2 P(O)R2
Scheme 19
O–
LHMDS TMS TMS
RCHO R N R N
TMS
Scheme 20
O OH
TMS BuLi, THF, –78 °C TMS
R1 N R1 N
TMS TMS
R2 R1
R2CH2CO2Et, LDA
TMS
R1 N
THF, < –70 °C NH
O
Scheme 21
A detailed coverage of the methods available for the preparation of N!silylimines\ their mechanism
of formation\ and their structure\ is presented in an article by Colvin et al[ on the condensations of
silyl ketene acetals with N!silylimines ð77T3046Ł[ N!Silylimines are also available via the condensation
reactions between N!"trimethylsilyl#phosphimines and carbonyl compounds ð65CB0380Ł and the
reaction of nitriles with organometallic reagents when quenched with TMS!Cl ð56JOM"8#120Ł[
As mentioned earlier\ N!silylimines provide a valuable alternative to oxime ethers for the synthesis
of N!unsubstituted b!lactams\ as the silyl group is readily removed by protodesilylation during
workup[ N!Silylimines are similar in reactivity and stereoselectivity to N!arylimines in their reactions
with enolates and silyl ketene acetals[
Like acyclic imines\ they exist in one geometrical form\ presumably the "E#!isomer[
Pioneering investigations by Hart et al[ have provided much insight into the scope and stereo!
selectivity of enolate!N!silylimine condensations[ In their original paper\ the viability of these
reactions was demonstrated using mainly a\a!disubstituted esters\ which add via their lithium
enolates to nonenolizable N!silylimines to a}ord mixtures of diastereomeric N!unsubstituted
b!lactams\ following aqueous workup "Equation "10## ð72JOC178Ł[ For a review of this aspect of
N!silylimine chemistry\ see Kleinman and Volkman ð80COS"1#823Ł[
R2 R3
R2 LDA, THF, –78 °C; R3CHN-TMS R1 (21)
R1 CO2Et NH
O
Scheme 22
Copyright # 1995, Elsevier Ltd. All R ights Reserved Comprehensive Organic Functional Group Transformations
3.12
Imines and Their N-Substituted
Derivatives: Hydrazones and
Other 1NN Derivatives
Including Diazo Compounds
J. STEPHEN CLARK
University of Nottingham, UK
2[01[0 HYDRAZONES AND THEIR DERIVATIVES 333
2[01[0[0 Hydrazones and Azines Derived from Hydrazine 333
2[01[0[1 N!Substituted and N\N!Disubstituted Hydrazones 335
2[01[0[2 Hydrazones from Azo Compounds 337
2[01[0[3 Semicarbazones 338
2[01[0[4 Osazones 349
2[01[0[5 Cyclic Hydrazone and Azine Derivatives 340
2[01[0[5[0 1!Pyrazolines and 1!pyrazolin!4!ones 340
2[01[0[5[1 Tetrahydropyridazines 342
2[01[0[5[2 Cyclic azines 342
2[01[1 R1C1NX FUNCTIONS "XP\ As\ Sb\ Bi\ Si\ Ge\ B or METAL# 344
2[01[1[0 Imines Substituted with Phosphorus or Arsenic 344
2[01[1[1 Imines Substituted with Silicon\ Germanium\ Tin or Lead 345
2[01[1[2 Imines Substituted with Boron or Aluminium 346
2[01[1[3 Imines Substituted with Lithium 348
2[01[1[4 Imines Substituted with Beryllium or Ma`nesium 348
2[01[1[5 Imines Substituted with Titanium\ Zirconium or Hafnium 359
2[01[1[6 Imines Substituted with Molybdenum or Tun`sten 359
2[01[1[7 Imines Substituted with Man`anese 359
2[01[1[8 Imines Substituted with Iron 359
2[01[1[09 Imines Substituted with Platinum or Rhodium 350
2[01[1[00 Imines Substituted with Zinc 350
2[01[2 DIAZO COMPOUNDS 350
2[01[2[0 General Methods for the Preparation of Diazo Compounds 350
2[01[2[1 Alkyl and Aryl Diazo Compounds 351
2[01[2[1[0 Diazotization of amines 351
2[01[2[1[1 Forster reaction of oximes 352
2[01[2[1[2 Dehydro`enation of hydrazones 352
2[01[2[1[3 BamfordÐStevens reaction of tosyl hydrazones 353
2[01[2[1[4 Cleava`e of N!nitrosoamines 354
2[01[2[1[5 Diazo `roup transfer 356
2[01[2[2 a!Diazo Carbonyl and b!Dicarbonyl Compounds 357
2[01[2[2[0 Diazotization of a!amino carbonyl compounds 357
2[01[2[2[1 Forster reaction of a!keto oximes 358
2[01[2[2[2 Direct nitrozation of carbonyl compounds 358
2[01[2[2[3 Dehydro`enation of a!keto hydrazones 358
2[01[2[2[4 BamfordÐStevens reaction of a!keto tosyl hydrazones 369
332
333 Hydrazones and Other 1NN Derivatives
2[01[2[2[5 Cleava`e of N!nitrosoamides 360
2[01[2[2[6 Diazo `roup transfer to carbonyl compounds 360
2[01[2[2[7 Substitution at the diazo carbon of a!diazo carbonyl compounds 363
2[01[2[3 a!Diazo Imines\ Amidines\ Imidates and Nitriles 365
2[01[2[3[0 a!Diazo imines 365
2[01[2[3[1 a!Diazo amidines and imidates 366
2[01[2[3[2 a!Diazo nitriles 366
2[01[2[4 Diazo Alkanes Containin` Heteroatoms at the Diazo Carbon 367
2[01[2[4[0 Diazo alkanes substituted with halo`ens 367
2[01[2[4[1 Diazo alkanes substituted with sulfur 367
2[01[2[4[2 Diazo alkanes substituted with nitro`en 368
2[01[2[4[3 Diazo alkanes substituted with phosphorus 379
2[01[2[4[4 Diazo alkanes substituted with arsenic\ antimony or bismuth 371
2[01[2[4[5 Diazo alkanes substituted with silicon\ `ermanium\ tin or lead 371
2[01[2[4[6 Diazo alkanes substituted with boron or thallium 374
2[01[2[4[7 Diazo alkanes substituted with lithium or sodium 374
2[01[2[4[8 Diazo alkanes substituted with ma`nesium 375
2[01[2[4[09 Diazo alkanes substituted with transition metals 375
2[01[2[4[00 Diazo alkanes substituted with silver 376
2[01[2[4[01 Diazo alkanes substituted with zinc\ cadmium or mercury 377
2[01[2[5 Unsaturated Diazo Alkanes 377
2[01[2[5[0 Diazo alkylidenes 377
2[01[2[5[1 a\b!Unsaturated diazo alkanes 378
2[01[2[5[2 Diazo alkynes 389
R1 R2
O H2NNH2 (<1 equiv.), EtOH, reflux
N
N
R1 R2
R1 R2
H+, EtOH
(R1R2CO)
H2NNH2 (excess) NH2
N H2NNH2 (excess)
EtOH, reflux
EtOH, reflux
R1 R2
R1, R2 = H, alkyl, aryl
Scheme 1
Arylalkyl ketones can be converted into hydrazones by treatment with hydrazine in an alcoholic
solvent\ but the azine product predominates in the presence of acids ð35JA0872\ 47CB491\ 50JCS4459Ł[
The formation of hydrazones of diaryl ketones usually requires prolonged reaction times and high
temperatures ð18CB1022\ 35JA803\ 44OSC"2#240Ł\ and in some cases it is necessary to add a water!
absorbing agent to the reaction ð49JA1789Ł[ Azines can be prepared by the addition of a mineral
acid to alcoholic solutions of hydrazones at room temperature ð49JA1789Ł\ or by heating hydrazones
Hydrazones 334
with ketones in the presence of acids "Scheme 0# ð0899CB1359\ 47JA2937Ł[ The latter method is useful
for the preparation of unsymmetrical azines[
N!Unsubstituted hydrazones can also be prepared by exchange reactions of N\N!dialkyl hydra!
zones with hydrazine ð55JOC566Ł[ This procedure avoids the problem of azine formation frequently
encountered when aldehydes or ketones are treated directly with hydrazine[ The carbonyl compound
is usually _rst converted into the corresponding N\N!dimethyl hydrazone\ and this compound is
then treated with hydrazine to give the required hydrazone "Scheme 1# ð55JOC566Ł[
O NMe2 NH2
Me2NNH2 (anh.) N H2NNH2 (excess) N
R1 R2 EtOH, reflux
R1 R2
EtOH, reflux
R1 R2
Scheme 2
An unusual example of hydrazone formation is the reaction of the cyclic nitrone "1# with hydrazine
to a}ord the ring!contracted hydrazone "0# "Scheme 2# ð56AJC228Ł[ In this case\ hydrazine attacks
the carbon centre adjacent to nitrogen rather than the carbonyl group\ and subsequent ring closure
then gives "0#[ In contrast\ the nitrone "1# reacts with 1\3!dinitrophenylhydrazone to give "2#\ the
expected hydrazone product[
O 2N NO2
NH2 O H
N
N H2NNH2 (anh.) Brady's reagent
+ + N
N C6H6 N EtOH, H2SO4
O– O– +
N
O–
(1) (2) (3)
Scheme 3
There are several routes to azines from compounds other than aldehydes and ketones[ For
example\ symmetrical azines can be formed by hydrogenation of nitriles with Raney nickel in
hydrazine "Scheme 3# ð44G0694\ 51JOC2605Ł[ This sequence proceeds by addition of hydrazine to the
nitrile to a}ord an imino hydrazide "3#\ followed by reduction and elimination to give a hydrazone\
which reacts with more of the nitrile to give "4#\ and _nally conversion to the symmetrical azine[
H NH2 NH2
H2NNH2 N Raney Ni, H2 N RCN
R CN
–NH3
R NH R
(4)
R NH R
Raney Ni, H2
N N
N H N
–NH3
R R
(5)
Scheme 4
Scheme 5
Scheme 6
Monoalkyl hydrazones derived from aromatic aldehydes have a labile N!hydrogen\ and addition
of the hydrazone to unreacted aldehyde is possible\ especially when the latter is in excess ð11JCS0537Ł[
The degree to which this side reaction occurs depends on the experimental conditions employed[
Aryl hydrazines such as phenyl\ p!nitrophenyl\ and o\p!dinitrophenyl hydrazine react with most
aldehydes or ketones to a}ord hydrazones\ and a large number of these compounds have been
prepared ð58QR26Ł[ N!Aryl hydrazones are usually solids\ and their melting points can be used to
identify the parent carbonyl compounds ð38JA2725\ 58QR26Ł[ N!Aryl hydrazones\ and especially
those substituted with nitro groups\ are stable to acids and are usually prepared under strongly
acidic conditions[
Reactions of aryl hydrazines with formaldehyde do not usually a}ord simple methylene hydra!
zones\ but it has been reported that the reaction of p!methylphenylhydrazine with formaldehyde
in acetic acid a}ords N!methylene!p!methylphenyl hydrazone as well as polymeric by!products
ð51CA"45#3534Ł[
Hydrazones can be prepared by exchange reactions of hydrazines with the imines derived from
aniline ð47M607Ł\ or with oximes ð45JOC533Ł "Scheme 6#[ Exchange reactions can also be performed
by treatment of the hydrazone of a low boiling ketone\ such as acetone\ with a less volatile aldehyde
or ketone "Scheme 6# ð47CA"41#8879Ł[ The reaction is forced to completion by the removal of the low
boiling ketone by distillation[
Tosyl hydrazones are useful precursors for the BamfordÐStevens and Shapiro reactions ð41JCS3624\
52JOC769Ł[ These compounds can be prepared by treatment of an aldehyde or ketone with tosyl
hydrazine under acidic or neutral conditions\ usually with ethanol or acetic acid as solvent[ Mono!
tosylhydrazones of a!diketones are important precursors to a!diazoketones "see Section 2[01[2[2[4#\
and they can be prepared directly by treatment of a!diketones with tosyl hydrazine ð47JA1146Ł[
Substituted tosyl hydrazines can be converted directly into hydrazones by treatment with base
ð50JCS0632\ 53JA1284Ł[ When N!aryl!N!benzyl!N?!tosyl hydrazines are heated with aqueous or
alcoholic alkali\ they rearrange to hydrazones with intramolecular migration of the benzyl group
"Scheme 7# ð50JCS0632Ł[ The same reaction can be accomplished by heating sodium salts of ben!
zenesulfonyl hydrazones in diethylene glycol ð53JA1284Ł[
Oxidation reactions of hydrazines can be useful for the preparation of hydrazones[ Treatment
Hydrazones 336
R3
OH N Ph
N H2NNR3R4 H2NNR3R4 N
N R4
solvent, heat solvent, heat
R1 R2 R1 R2 R1 R2
R1R2CO
–Me2CO
R3
N
N R4
Scheme 7
Ph
–
N N+
Ph
–Ts–
Ts Ph Ts Ph Ph Ph
base
N N N N N N Ph N H
–
H Ph Ph Ph N
–Ts–
Ts Ph
N N
–
Ph
Scheme 8
of hydrazines with oxidising agents\ such as mercury"I# oxide ð00JPR011\ 53CRV038Ł\ or bromine
ð51JOC2835Ł\ under carefully controlled conditions\ a}ords either hydrazone or azine products[
Oxidation of trimethylhydrazine with bromine a}ords the hydrobromide salt of formaldehyde
dimethylhydrazone "Equation "0## ð51JOC2835Ł[ In certain cases\ rearranged hydrazones may be
obtained from oxidation reactions[ For example\ the hydrazone "8# is obtained via the azo compound
"7# produced by oxidative rearrangement of N!benzyl!N!phenylhydrazine with mercury"I# oxide
"Scheme 8# ð53CRV038Ł[
Me Me Me
HBr, Br2, heat
N N N N HBr (1)
Me H Me
Ph Ph H Ph
HgO
N NH2 N N N N
Ph Ph Ph
(8) (9)
Scheme 9
NH2 NH2
– N N
H2NNH2 H3O+
H2N NH– + Ph Ph
Ph Ph
Ph Ph
(10)
Scheme 10
Ar
Y Ar N Y
+ –CO2 N
Ar N N – N N H
Z Z = CO2H
Z
Y
Ar N Y
N
H Z
Y, Z = electron-withdrawing groups
Scheme 11
When a compound containing an activated methine group is coupled to an aryl diazonium ion\
the intermediate azo compound cannot tautomerize[ If one of the activating groups is an acyl or
carboxyl group\ this is cleaved by hydrolysis on workup "Scheme 01#[ This reaction is known as the
JappÐKlingemann reaction\ and there are many examples of its utility ð48OR032Ł[ For those sub!
strates in which there is more than one cleavable activating group\ the acyl group corresponding to
the weaker acid is usually lost ð91CB804Ł[ The tendency of various activating groups to undergo
cleavage is illustrated by the behaviour of various a!substituted cyclohexanones "Scheme 02#[ The
side chain is cleaved when it is either a carboxyl or formyl group\ but when the side chain is an ester
or acetyl group\ ring scission is observed ð48OR"09#032Ł[ It is possible to isolate the azo intermediates
formed during the JappÐKlingemann reaction\ by performing addition at low temperature in
weakly acidic media ð42LA"468#17\ 46CB0959\ 48OR032\ 51JA2403\ 51JA3776\ 51JA3781\ 54JCS6074Ł[ Hydrolytic
Hydrazones 338
cleavage of these azo intermediates is catalysed by acid or base\ and nucleophilic reagents such as
ethanol\ phenol or aniline also promote this reaction ð51JA2403Ł[
HO H Ar
Y
+ R1
Ar N N R1 – Ar N Y N
N N H
R2
O –OH
O R2 Y R1
Y = electron-withdrawing group
Scheme 12
O
N Ar
N
Y = H, OH H
O O
O O
ArN2+X–, base Y
Y N
N
Ar Y = R, OR H Ar
O N O
N
HO R
Scheme 13
Compounds activated by nitro rather than acyl groups react with aryl diazonium salts to a}ord
hydrazones ð42LA"468#17Ł[ Primary nitroalkanes react to give the corresponding aryl hydrazones of
a!nitro aldehydes ð48OR"09#0Ł[ For example\ nitromethane reacts with benzenediazonium salts in dilute
hydrochloric acid "pH 3[4# to give the phenyl hydrazone of nitroformaldehyde ð37JA0270Ł[ When
aryl dinitromethanes and diaryl nitromethanes react with benzenediazonium ion\ the nitro group
migrates to the aromatic ring and p!nitrophenylhydrazones are produced "Scheme 03# ð48OR"09#0Ł[
In cases where the para position is blocked\ the nitro group migrates to the ortho position[
H Ar
Ar Ph Ar
Y
ArN2+ X–, base N N N
N Y
NO2 Y NO2 H
O 2N
Y = Ar, NO2
Scheme 14
Aryl diazonium salts will also couple with a variety of unsaturated compounds to a}ord aryl
hydrazones ð48OR0Ł[ For example\ enamines couple e.ciently with aryl diazonium salts[ Substrates
with a hydrogen atom on the b!carbon a}ord glyoxal b!arylhydrazones\ and those without a
hydrogen atom on the b!carbon are cleaved to furnish ketone hydrazones "Scheme 04# ð45JA4473Ł[
2[01[0[3 Semicarbazones
Semicarbazones and thiosemicarbazones can be prepared by treatment of a ketone or aldehyde
with semicarbazide or thiosemicarbazide "Scheme 05#[ The reaction is general acid catalysed\ and
the yield of semicarbazone and the rate of reaction are dependent on the pH of the reaction medium
ð21JA1770\ 48JA364\ 55BSB590Ł[ The formation of semicarbazones from ketones can be catalysed by
the addition of anilines ð51JA715Ł[ In this case\ a Schi} base is formed as an intermediate which
then undergoes exchange with semicarbazide in a subsequent step "Scheme 05#[ The rate of reaction
349 Hydrazones and Other 1NN Derivatives
Ar
R3
H N
N H + N CHO
R1 and R2 = alkyl
R3 R3
R1 R2
+ R1 N R3
Ar N N X– +
N Ar
R3
R2 C H N
R 2= H H N + N H
O R3
R1
Scheme 15
of semicarbazide with the intermediate imine is much greater than on the parent carbonyl compound
ð47M607\ 51JA715Ł[
X NH2
O H2NNHC(X)NH2
N
N H
R1 R2
R1 R2
ArNH2
H2NNHC(X)NH2
Ar
N
R1 R2
Scheme 16
Aliphatic and aromatic nitriles can be converted into semicarbazones of the corresponding
aldehydes by reduction with Raney nickel in the presence of semicarbazide ð44CB0845\ 48JA1404Ł[
This reaction is analogous to that used to prepare azines from nitriles and hydrazine "see Section
2[01[0[0#[
2[01[0[4 Osazones
Osazones are formed by the addition of hydrazines to a!diketones or a!hydroxy ketones[ These
compounds have been known since the early days of carbohydrate chemistry\ when Fischer _rst
isolated sugar phenylosazones ð0773CB468\ 0776CB710Ł[ Sugar osazones have a {quasi!aromatic| struc!
ture "00#\ _rst proposed by Fieser and Fieser "Equation "1## ð52ACS448\ 54AG479\ 54AG"E#463\ 54JA485Ł[
This structure accounts for the di}erences in spectral and chemical properties in comparison to
nonsugar osazones ð54AG479\ 54AG"E#463Ł[ In aqueous or alcoholic solutions\ reactions of aryl
hydrazines bearing electron!withdrawing substituents\ with aldoses or ketoses a}ord the cor!
responding hydrazones ð47CB1534Ł[
Ph
CHO N H Ph
H N N
CHOH
N
CHOH PhNHNH2
(2)
CHOH CHOH
CHOH CHOH
CH2OH CHOH
CH2OH
(11)
Hydrazones 340
During osazonization of sugars by phenylhydrazine\ hydrazone formation occurs with oxidation
of the hydroxyl group adjacent to the carbonyl group\ but the other hydroxyl groups are una}ected[
However\ reactions of sugars with N!methyl!N!phenylhydrazine give osazones in which the quasi!
aromatic structure cannot be formed\ and all primary and secondary hydroxyl groups are converted
into hydrazones ð53JA621Ł[
Osazones may be prepared from a!diketones by treatment with an excess of a substituted hydra!
zine\ or from a!hydroxy\ a!halo\ a!methoxy\ a!acetoxy and a!dialkylamino ketones "Scheme 06#[
The reaction of aryl hydrazines with a!hydroxy ketones or aldehydes leads to formation of aryl
hydrazones\ osazones\ or both[ The ratio of products is dependent on the stoichiometry of reactants\
the experimental conditions employed\ and the structure of the reactants[ Several alternative mech!
anisms have been proposed to account for the formation of osazones from a!hydroxy ketones
ð25CB230\ 41JA3220\ 55JA2754Ł[ Hydrazones are produced in the presence of strong acids ð46CB241\
47CB1534\ 52CB540\ 52CB547Ł\ but in mildly acidic media both the hydrazone and osazone products
may be obtained[ In aqueous acetic acid\ the proportion of osazone to hydrazone rises with
increasing acid concentration ð52CB547Ł[ Hydrazones rather than osazones are favoured in neutral
aqueous or alcoholic solutions ð46CB241\ 52CB540Ł[
R4
R4 N
O R3 N O
N
R3R4NHNH2 R3 N R3R4NHNH2 R2
R2 + R2
R1 R1 R1
R2
O R1 N R3 X
O N
R4
X = OH, Cl, Br, OMe, OAc, NR2
Scheme 17
a!Halo carbonyl compounds react with hydrazines to give hydrazones or osazones depending on
the structure of the reactants\ stoichiometry and the experimental conditions used ð41JA3220Ł[ For
example\ Brady|s reagent reacts with a variety of a!halocycloalkanones at room temperature to
furnish the corresponding a!halo hydrazones\ and osazones can be prepared from these a!halo
hydrazones by heating them with an excess of the reagent ð41JA3220\ 44JA0992Ł[ In contrast\ treatment
of dichloroacetaldehyde with either phenyl hydrazine or o\p!dinitrophenyl hydrazine a}ords only
the corresponding glyoxal osazones ð29JCS85\ 50JOC468Ł[ In general\ if the hydrazone of an a!halo
aldehyde is required\ the reaction should be performed in a concentrated mineral acid ð50JOC468Ł[
The a!halo hydrazones are very reactive and will react with methanol to a}ord a!methoxy
hydrazones ð41JA3220\ 44JA0992Ł\ and with acetic acid to give a!acetoxy hydrazones ð42JA5915Ł[ a\b!
Unsaturated hydrazones can be formed by elimination reactions of these compounds ð41JA3220Ł[
Aryl hydrazines oxidise benzylic or allylic primary and secondary alcohols to give ketones which
then react further to a}ord hydrazones ð40JCS0651\ 47JOC1903Ł[ The reaction is acid catalysed and
osazone formation is favoured when aryl hydrazines with electron!withdrawing substituents are
used ð25CB230\ 49JCS0217Ł[ The mechanism of this reaction is similar to that proposed for the
formation of sugar osazones ð41JCS550Ł[
Ph
Ph
PhNHNH2 Ph
Ph (3)
EtOH, reflux N N
O
Ph
(12) (13)
Many b!substituted ketones will react with hydrazine or aryl hydrazines to give 1!pyrazolines[
The reaction can be performed using b!chloro ð25JA1949\ 42JCS1723\ 50CA"44#06415Ł\ b!bromo
ð42JCS1723Ł\ b!seleno ð40JA0963Ł\ b!hydroxy ð12CB0025Ł and b!amino ketones ð13CB0097\ 34JCS015\
41JCS0210Ł "Equation "3##[
O X R5
R5NHNH2 N N
(4)
R1 R4 EtOH, reflux R1 R4
R2 R3
R2 R3
1!Pyrazolines can also be prepared by 0\2!dipolar cycloaddition reactions with alkenes[ For
example\ nitrilimine "05# can be generated from either the tetrazole "03# or the a!chloro imine "04#\
and reacts readily with the alkene "06# to a}ord the 1!pyrazoline "07# in good yield "Scheme 07#
ð51T2Ł[ Many other alkenes can participate in this reaction ð51T2Ł[
N Ph
Ph N
N N heat, 15 0–160 °C
Ph
–N2 H
(14)
+ – (17)
Ph N N Ph N
N
(16) H
Ph Et3N, C6H6, 20 °C Ph
(18)
N
N H
Ph Cl
(15)
Scheme 18
R1 R2 R2 R1
R2 R1
N HCO2H
N N R2 + N R2 (5)
N N
R1 R2 R1 R1
CHO CHO
Acetone azine can be converted to a 1!pyrazoline hydrochloride salt by reaction with methyl!
magnesium bromide followed by treatment with dilute hydrochloric acid "Equation "5## ð51JOC1654Ł[
The reaction is presumed to occur by a!deprotonation by the Grignard reagent followed by cycli!
zation\ but the same reaction has been reported to yield t!butylhydrazine as the major product
ð30LA"436#0Ł[
Hydrazones 342
i, MeMgBr
N N (6)
N HCl
ii, HCl (aq.) N
H
There are many methods for the preparation of 1!pyrazolin!4!ones\ the most general being the
reaction of hydrazines with b!aldehydo or b!keto esters "Equation "6##[ A variety of substituents
can be present in the dicarbonyl compound\ and b!thiono esters\ b!oximino esters and b!keto amides
can be used[ In general\ substrates with small substituents give the highest yields\ and reactions fail
when R0 and R1 are both very large[ The reaction is usually performed by heating the dicarbonyl
compound with the hydrazine at 099Ð199>C\ without the addition of a catalyst[ Formation of the
hydrazone occurs at lower temperatures than those required to accomplish cyclization\ and hydra!
zone formation and cyclization can be performed in separate reactions if required ð42CJC0914Ł[
Acids and bases can be used to promote the cyclization reaction ð37JA0879Ł[
R5
O O
N N
+ H2N NHR5 (7)
R1 OR4 R1 O
R2 R3
R2 R3
R1–R3 = H, alkyl, aryl; R4, R5 = alkyl, aryl
1!Pyrazol!4!ones can be prepared by treatment of alkynyl acids\ esters or amides with phenyl
hydrazine "Equation "7## ð30JA0040Ł[ b!Alkoxy!\ b!alkylthio! and b!acylthio!a\b!unsaturated esters
react with hydrazine in a similar manner[ 1!Pyrazol!4!ones can also be prepared by reaction of
many other heterocyclic compounds with hydrazine\ as summarized in Scheme 08[
Ph
O N N
R1 + H2N NHPh (8)
X R1 O
2[01[0[5[1 Tetrahydropyridazines
0\3\4\5!Tetrahydropyridazin!5!one "10# can be prepared from the hydrazone "19# formed by
treatment of the g!keto nitrile "08# with a diazo compound[ Treatment of hydrazone "19# with HBr
in acetic acid leads to the formation of "10# in good yield "Scheme 19# ð58LA"615#70Ł[
0\3\4\5!Tetrahydropyridazin!3!ones "12# can be prepared by JappÐKlingemann reaction of g\d!
unsaturated b!keto esters and b!diketones "Scheme 10# ð79S512Ł[ The reaction proceeds via the
intermediate hydrazone "11#[
0\3\4\5!Tetrahydropyridazines can be prepared by ð3¦1Ł!cycloaddition reactions[ For example\
the diazadiene "13# generated from an a!chloro hydrazone\ undergoes an inverse!electron!demand
DielsÐAlder reaction with cyclopentene to give the cycloaddition product "14# in good yield "Scheme
11# ð66TL006Ł[
An unusual example of the preparation of 0\3\4\5!tetrahydropyridazine involving ring expansion
of pyrrolidine has been reported ð54JA282Ł[ Treatment of pyrrolidine with Angeli|s salt a}ords
0\3\4\5!tetrahydropyridazine\ presumably by formation and rearrangement of the diazene "15#
"Scheme 12#[ This reaction is of limited synthetic value\ and is not successful when piperidine or
morpholine are used as substrates ð54JA282Ł[
NH2
〈54CA3342〉
HO N OH H2NNH2
N O
N Ph O
H2NNH2 H2NNH2
〈24CR(178)811〉 〈1893CB2053〉
H
N N
R1 O
H2NNH2 R2 H2NNH2
O O O O
EtO2C H2NNH2
O O
〈54JA4931〉 HO2C O O 〈1894CB970, 05CB2023〉
〈1894CB970〉
Scheme 19
Cl
Cl CN
O HO CN
O i, HBr, HOAc
+
N ii, H2O
Cl N
Cl N2 CO2Et
H CO2Et
(19) (20)
Cl
HO
N CO2Et
Cl N
O
(21)
Scheme 20
R2 O O O O
R2 O O
ArN2+ X– R1 Y Y
R1 Y R1 N
H N
R3 N N
R2 Ar
Ar
(22) (23)
Scheme 21
R1C1NX Functions 344
Cl CO2Me CO2Me
H
CO2Me NaHCO3 (aq.), Et2O (17)
N H N N
N N N
H
CONH2 CONH2 CONH2
(24) (25)
Scheme 22
Na2ONNO2 +
N N N
H N
N– H
(26)
Scheme 23
the preparation of larger cyclic azines[ For example\ the diazepine "17# can be synthesized in good
yield by reaction of 0\4!diketones such as "16# with hydrazine "Equation "09## ð45JA3369Ł[
R2 R2
H2NNH2
(9)
O N
R1 O R1 N
R2 R2
H2NNH2
O N (10)
O N
R1 R1
(27) (28)
CHO
H2NNH2 N N N
N N
N
CHO N
N
(29) (30)
Scheme 24
2[01[1 R1C1NX FUNCTIONS "XP\ As\ Sb\ Bi\ Si\ Ge\ B or METAL#
Scheme 25
Because of the problems associated with the preparation of N!silyl imines from enolizable carbonyl
compounds\ several alternative methods of preparing these compounds have been developed[ Enol!
izable N!trimethylsilyl aldimines can be prepared in good yield by treatment of "TMS#1NCHO with
organolithium reagents at low temperature "Scheme 15# ð78TL3164Ł[ N!Silyl imines can also be
prepared by the reaction of silyl chlorides with N!lithio imines ð56JOM"8#120\ 61IC131\ 62JCS"D#046\
65JCS"D#0Ł\ iminoborates ð65JOM"007#C0Ł\ iminoaluminates ð75TL0584Ł\ or N!trialkylstannyl imines
"Scheme 16# ð89PAC594Ł[
Scheme 26
Li SiR3 SnR3
N R3SiCl, –LiCl N R3SiCl, (R3Sn)2O N
–[(R3Sn)3O]+ Cl–
R1 R2 R1 R2 R1 R2
R3SiCl
–LiCl, –Al(OR)3 (R2 = H)
Al(OR)3Li
N
R1
Scheme 27
R1C1NX Functions 346
Enolizable N!trimethylsilyl aldimines can be synthesized in good yield by vacuum gasÐsolid
reactions "VGSR# in which a!"N!silylamino#nitriles are dehydrocyanated on solid potassium hydr!
oxide "Scheme 17# ð77TL0176Ł[
Scheme 28
TMS TMS
N O CH2Cl2, Et2O N
P + (11)
Ph Ph F3C CN –Ph3PO F3C CN
Ph
(31) (32) (33)
N!Germyl imines can be prepared by reaction of alkyl germanium chlorides or GeX3 "XCl\
Br# with N!lithio imines ð56JOM"8#120\ 60JA5692\ 62JCS"D#046\ 65JCS"D#0Ł\ and mixed imino germyleneÐ
chromium complexes such as "CO#4CrGe"Cl#NCPh1 and "CO#4CrGe"NCPh1#1 can be synthesized by
reaction of one or two equivalents of Et2GeNCPh1 with Cl1GeCr"CO#4 = THF at room temperature
ð76JOM"220#00Ł[
N!Stannyl imines are easily synthesized by reaction of alkyl tin halides or SnX3 "XCl\ Br# with
N!lithio imines ð56JOM"8#120\ 62JCS"D#040\ 62JCS"D#046\ 65JCS"D#0Ł[ These compounds can also be
prepared directly from the corresponding aldehyde or ketone by treatment with N"SnMe2#2 "Scheme
18# ð89PAC594\ 80SL132Ł[ Because of the low basicity of N"SnMe2#2\ enolizable carbonyl compounds
are not deprotonated\ and N!stannyl imines are obtained in good yield ð89PAC594Ł[
Me3Sn SnMe3
O Me3Sn
N OSnMe3 –(Me3Sn)2O N
+ N SnMe3 Me3Sn
R1 R2 Me3Sn R2 R2
R1 R1
Scheme 29
It has been reported that the N!plumbyl imine Ph2PbNCPh1 can be prepared by reaction of
LiNCPh1 with Me2PbCl ð56JOM"8#120Ł[ However\ only impure material was obtained\ and the
compound was not fully characterized[
R2
R2
THF, RT B
R1 CN + H B N R3 (13)
R3
R1
R1 = alkyl, aryl; R2, R3 = H, alkyl
Many N!boryl imines have been prepared by the reaction of haloboranes with N!trialkylsilyl or
N!lithio imines\ or from free imines "Scheme 29# ð57CC149B\ 69JCS"A#1909\ 61JCS"D#269Ł[ Good yields
of N!boryl imines can be obtained using this method ð61IC131Ł[
Li BRnX2–n H
N BRnX3–n, –196 °C to RT N BRnX3–n, toluene, reflux, –HX N
R1 R2 R1 R2 R1 R2
Scheme 30
N!Alumino imines are useful precursors for the synthesis of other substituted imines and can be
prepared by a variety of routes ð89PAC594Ł[ The simplest method of preparing aluminum aldimines
is by treatment of nitriles with diisobutylaluminum hydride "Equation "03## ð89JOC3088Ł[ A large
number of aluminum imines have been prepared from nitriles ð56AG"E#792\ 56AG707\ 82JOM"345#050Ł\
or cyanohydrins in this manner ð89TL2370\ 82T2798Ł[
Bui
Bui
C5H12, –78 °C Al
R CN + Al H Bui N (14)
Bui
R
R = alkyl, aryl
Aldimino aluminates can be prepared in good yield by partial reduction of aromatic and aliphatic
nitriles with lithium triethoxyaluminum hydride ð53JA0974\ 75TL0584Ł[ Lithium aluminum hydride
can be used to perform the same reaction\ but overreduction can be a problem with certain substrates
ð53JA0974Ł[ Sodium or lithium trialkylaluminum hydrides of the type M¦"R02AlH#− "MLi\ Na\
R0 Et\ Bui# react with nitriles of the type R1CN "R1 Et\ Pr\ Ph\ p!MeC5H3\ p!MeOC5H3\ c!C5H00\
PhCHCH\ 1!furyl\ 1!thienyl# to give the imino aluminates M¦"R02AlNCHR1#− ð65JOM"007#C2\
¦ t −
77JCS"P0#834Ł[ The aluminate Li ðAl"NCBu 1#3Ł can be prepared by reaction of aluminium chloride
t
with four equivalents of LiNCBu 1 ð60CC0164Ł[
N!Alumino ketimines can be prepared by the addition of trialkylaluminum reagents to nitriles[
Addition of a trialkylaluminum to an alkyl or aryl nitrile furnishes complex "23# which rearranges
to the corresponding dimeric N!alumino ketimine "24# in good yield when heated to 099Ð199>C
"Scheme 20# ð53CB1550\ 54JCS1551\ 54JCS4972Ł[
The gallium!substituted imines "Et1GaNCHPh#1 and "Et1GaNCHBut#1 can be synthesized by
thermal rearrangement of the complexes produced by reaction of GaEt2 with PhCN or ButCN
ð56JCS"A#0111Ł[ These reactions are analogous to those of trialkylaluminum reagents with nitriles[
R1C1NX Functions 348
R2 R 2
R1 Al R2
100–200 °C
2R1 C N + AlR23 2R1 C N AlR2 3 N N
R2 Al R1
R2 R2
(34) (35)
Scheme 31
MgI
N
R2 Mg, Et2O, reflux R2
R1 R1 R1
I IMg ( )n
( )n CN ( )n CN R2
n = 1, 2; R1 = H, alkyl; R2 = alkyl
Scheme 32
359 Hydrazones and Other 1NN Derivatives
2[01[1[5 Imines Substituted with Titanium\ Zirconium or Hafnium
Several titanium and zirconium N!metallo ketimines are known[ The complexes Cp1MCl"NCR1#
and Cp1M"NCR1#1 "MTi\ Zr and RPh\ p!MeC5H3\ But# can be prepared by treatment of
titanocene or zironocene dichloride with either one or two equivalents of an appropriate N!lithio
ketimine in diethyl ether ð60MI 201!90Ł[ Forcing conditions are usually necessary for successful
addition of a second equivalent of the N!lithio ketimine\ and with bulky substrates\ such as LiNCPh1
and LiNCBut1\ the second chlorine on titanium is not replaced[ The complexes Cp1TiClðNC"CF2#1Ł
and Cp1TiðNC"CF2#1Ł1 have been prepared in an analogous fashion by treatment of titanocene
dichloride with one or two equivalents of LiNC"CF2#1 ð60CC104\ 60MI 201!90Ł[
The compound Cp1TiCl"NCPh1# can be prepared by reaction of titanocene dichloride with
Me2SiNCPh1 in xylene at re~ux\ with removal of the trimethylsilyl chloride produced during the
reaction ð60MI 201!90Ł\ and Cp1TiClðNC"CF2#1Ł can be obtained by treatment of titanocene dichloride
with Me2SnNC"CF2#1 in benzene at re~ux ð62JCS"D#040Ł[
The complexes Cp1Zr"NCPh1#1\ Cp1Hf"NCPh1#1 and Ti"NCPh1#3 can be synthesized by treatment
of Cp1Zr"NMe1#1\ Cp1Hf"NEt1#1 and Ti"NMe1#3 with either two or four equivalents of HNCPh1 in
diethyl ether at re~ux ð60MI 201!90Ł[
A more general approach to the synthesis of iron!substituted imines involves reaction of iron
complexes of the type CpFe"CO#1X "XCl\ Br\ I#\ or Fe"CO#3X1 "XBr\ I#\ with N!lithio ketimines
at low temperature ð63JCS"D#0519Ł[ The complexes CpFe"CO#"NCBut1#\ ðFe"CO#2"NCPh1#Ł1\
Diazo Compounds 350
"Fe"CO#2ðNC"3!MeC5H3#1Ł#1\ ðFe"CO#2"NCPhBut#Ł1\ Fe1"CO#5I"NCPh1#\ Fe"CO#5I"NCPh1#\ Fe"CO#5
IðNC"3!MeC5H3#1Ł\ and Fe"CO#5I"NCPhBut# have been prepared in low yield by this route
ð63JCS"D#0519Ł[
O O ZnBr
O N
Br Zn, THF, reflux ZnBr R3CN, THF, reflux
R1O R1O R1O R3
R2 R2 R2
Scheme 33
Dialkyl zinc reagents add to benzonitrile to give zinc!substituted imines ð57JCS"A#46Ł[ Addition
of R1Zn "RMe\ Et\ Ph# to benzonitrile at low temperature\ followed by warming to room
temperature\ a}ords zinc complexes of the type "RZnNCPh1#1 "RMe\ Et\ Ph# ð57JCS"A#46Ł[ When
these complexes are heated to 79>C they disproportionate to give Zn"NCPh1#1 and R1Zn[
R1
N2
–H+ R2
R1 H+, HNO2 R1
NH2 N2+
R2 –2H2O R2
–N2 R1
(37)
+
R2
R1 or R2 = electron-withdrawing group
Scheme 34
Methylamine can be converted into diazomethane using nitrosyl chloride under basic conditions
"Scheme 24# ð59CB0430Ł[ In this case\ an intermediate nitrosoamine "27# is formed and activating
groups are not required[ Other diazo alkanes can be prepared by this reaction\ but careful control
of the stoichiometry is necessary in order to obtain good yields ð57ACS0722Ł[ The same trans!
formation can be accomplished by reacting an amine with nitrosyl chloride and then treatment of
the resulting diazohydroxide "28# with acetic acid and ammonia "Scheme 25#[ Partial decomposition
of the diazo compound by acetic acid may occur during the reaction\ and in many cases poor yields
of the diazo compound are obtained ð70ACS"B#068\ 71ACS"B#016Ł[
O– K+
N N
EtOK, –EtOH Me
NOCl, Et2O, –80 °C
H
KOH (aq.)
Me NH2 N NO
Me
(38) KOH (aq.) H2C N2+
Scheme 35
Diazo Compounds 352
OH
R1 MeCO2H R1 R1
NOCl, Et2O, –78 °C N N
NH2 N2+ N2 + MeCO2H
R1 –H2O
R2 R2 R2
R2
MeCO2–
(39)
Scheme 36
Scheme 37
R1 NH2
–'H2'
R1
N N2 (16)
oxidant
R2 R2
oxidant = HgO, AgO, MnO2, Pb(OAc)4, I2, NBS, Ph3Bi(CO)3
Mercury"II# oxide is often used to dehydrogenate hydrazones "Scheme 27#[ The reaction can be
performed in a variety of solvents\ and sodium sulfate can be used to trap the water liberated during
the reaction[ Addition of trace amounts of alcoholic KOH promotes the deprotonation step and
accelerates the reaction ð48JOC459Ł[ Mercury"II# acetamide and mercury"II# tri~uoroaetamide can
be used as dehydrogenating agents in some cases ð09JCS1045\ 48JOC274Ł[
H –
R1 NH2 R1 N Hg–OH R1
HgO R1 N Hg–OH KOH, –H+ –Hg, –HO–
N N N2
N
R2 R2 R2
R2
(41) (42)
Scheme 38
R1 R1 H R1
I2, R3N –R3NH+ I–
N NH2 N N N2
R2 R2 I R2
Scheme 39
Several other reagents can be used for the dehydrogenation of hydrazones to diazo compounds[
Reactions of metallated hydrazones with molecular oxygen have been used to prepare some simple
diazo compounds ð56JA4201Ł[ Nickel peroxide has found occasional use\ and good yields of the
diazo products have been obtained ð55CC629\ 70TL3826Ł[ N!Bromosuccinimide has been used to
accomplish dehydrogenation\ but signi_cant amounts of azines are formed which detract from the
synthetic utility of this reagent ð44JA0569Ł[ Triphenylbismuth carbonate has been used to prepare
diphenyldiazomethane from benzophenone hydrazone in excellent yield\ but the generality of this
reaction has not been explored ð68CC694Ł[
The BamfordÐStevens reaction of tosyl hydrazones derived from alkyl or aryl ketones is usually
achieved by heating the substrate with a base[ A variety of solvent and base combinations have
been used to e}ect the reaction ðB!75MI 201!90Ł[ Unfortunately\ the rather harsh conditions required
to promote the reaction often lead to low yields of sensitive diazo compounds[
The BamfordÐStevens reaction can also be accomplished by alkaline cleavage of methylsul_nyl
or 1!nitrophenylsulfenyl hydrazones ð64CC003\ 64TL0454Ł[ In the _rst case\ the diazo compound is
usually isolated after treatment of the unsubstituted hydrazone with methanesul_nyl chloride in the
Diazo Compounds 354
presence of two equivalents of triethylamine\ without isolation of the intermediate methylsul_nyl
hydrazone[
It is possible to transform aldehyde and ketone tosyl hydrazones to diazo compounds under
biphasic conditions ð66BSB628\ 67SC458Ł[ Triisopropyl benzenesulfonyl hydrazones may be used as
substrates in this reaction\ and they are cleaved more rapidly than the corresponding tosyl hydra!
zones ð71S308Ł[
Dialkyl diazo compounds are often unstable under the conditions of the BamfordÐStevens
reaction\ even when the reaction is performed in an aprotic solvent[ Vacuum pyrolysis of salts of
tosyl hydrazones is an alternative method for the preparation of these compounds ð54JA824Ł[ The
pyrolysis reaction is useful for the synthesis of aryl diazoalkanes\ but gives only low yields when
heat!sensitive diazoalkanes are produced[ Phenyldiazomethane can be prepared in good yield from
the sodium salt of benzaldehyde tosylhydrazone using this method ð75OS"53#196Ł[ The reaction can
also be performed by photochemical methods ð70JOC3574Ł[
–
O
–H2O
R
RO– N O
N O N +
N N2
O R N
O R HO N R
RO H
Scheme 41
HCHO O R2
O O R2
R2CH2NH4Cl NaNO2 KOH (aq.)
+ R1 N N
R1 NH2 –H2O R1 N N Cl– H
H H H N
O
O OH R2
+
R1 N N2
H
Scheme 42
Diazomethane and other diazo alkanes can be prepared by the cleavage of N!acyl!N!nitroso!
amines "Scheme 32#[ Urethanes\ ureas\ carboxamides\ arylsulfonamides and guanidines can be used
as precursors[ With urethanes and carboxamides\ nucleophilic attack of the base at the carbonyl
group leads to the formation of a diazotate ð51OS"30#05Ł[ The diazotate intermediates have been isolated
ð91CB786\ 59ZN"B#640\ 50AG110\ 52CB0601\ 54JOC3146\ 55JOC0971\ 57T1770Ł\ but are usually protonated in
situ to form diazohydroxides which are then converted diazonium ions[ The diazonium ion is either
deprotonated to a}ord the diazo compound or loses nitrogen and forms a carbonium ion[ The
355 Hydrazones and Other 1NN Derivatives
course of the reaction is in~uenced by the nature of the substituents present in the precursor
ð63ACR310Ł\ with branched alkyl groups favouring the formation of carbonium ions ð55JOC0971Ł[
When both substituents are primary alkyl groups\ the diazo alkane is produced along with products
arising from cationic species ð40LA"462#052\ 55JOC0971Ł\ but with methyl\ benzyl and allyl substituents\
diazo alkane formation is favoured ð91CB786\ 61TL4036\ 62JOC0710Ł[
R1
ROH, RO– R1 –HO–
R1 R2 –H+
R1 R2
X
N R2 N
HO N R2 N2+ N2
N
O
X = RO2C, R2NCO, RCO, ArSO2, (O2NNH)C=NH
Scheme 43
–
H2N NO K+ HN N O
N KOH, –H+ N
O R2 O R2
R1 R1
R1 N OH R1 R2
–H2O
N + KOCN
R2 N2
Scheme 44
H H
O2N N NO O2N N N O
KOH, –H+ –O2NNCN–K+
N N
HN R2 K+ – N R2
R1 R1
R1 N OH R1 R2
–H2O
N
R2 N2
Scheme 45
Diazo Compounds 356
Diazo alkanes have been prepared by base!promoted fragmentation reactions of N!alkyl!N!
nitrosocarboxamides[ For example\ treatment of N!methyl!N!nitrosoacetamide with potassium
hydroxide in methanol a}ords a solution of diazomethane ð42CB65\ 42CB167Ł[ The same trans!
formation can be e}ected using alkyllithium reagents ð50AG110Ł[ Diazomethane can also be prepared
by cleavage of N\N!dimethyl!N\N!dinitrosooxalamide with methylamine "Equation "06##[ Diazo!
methane may be distilled from the reaction mixture when a high boiling alcohol solvent is used\ or
can be generated and reacted in situ using methanolic potassium carbonate in the presence of an
appropriate substrate ð50CB1436Ł[
NO
O N O NHMe
Me MeNH2 or K2CO3, MeOH
+ 2H2C=N2 (17)
Me
O N O NHMe
NO
a\v!Bis"diazo# alkanes can be synthesized from the corresponding dinitroso compounds "Equation
"07##[ Although 0\1!bis"diazo#ethane has not been observed directly\ the existence of this compound
has been shown by trapping experiments ð43JA330Ł[ 0\2!Bis"diazo#propane has marginal stability in
solution and can be prepared by treatment of N\N?!dibenzoyl!N\N?!dinitroso!0\2!propanediamine
with sodium hydroxide in methanol ð58JA695Ł[
RO2C CO2R
N ( )n N base
N2 ( )n N2 (18)
NO NO
Longer chain a\v!bis"diazo# alkanes have been prepared and fully characterized ð49CB026\
43JA330Ł[A useful and high yielding route to 0\5!bis"diazo#hexane has been developed in which the
nitrosamide polymer formed by nitrozation of Nylon 55\ is treated with potassium hydroxide in
aqueous methanol "Equation "08## ðB!75MI 201!90Ł[
O ON N2
N KOH, MeOH, H2O, Et2O
N (19)
O NO N2
n
O N O O
KOH, ROH
S N H 2C N2 + S OR (20)
O Me O
R2 R2
R1 R2 N N2+ R1 R2 N R5
R5N3 R1 R1
N + R3
R3 R3
NR42 N N– N2 NR42
R3
R42N R5 R42N R5
Scheme 46
O O
NaNO2, H+
R1 R1 (21)
Y Y
NH2 N2
Y = R2, OR2, NR22
NO2 NO2 O
NH2 N2+ N2
Scheme 47
a!Diazo b!dicarbonyl compounds are readily accessible by diazotization of amines\ and there are
many examples which testify to the success of the reaction ðB!75MI 201!90Ł[ The side reactions
encountered during diazotization of a!amino ketones do not usually occur with a!amino!b!dicar!
bonyl compounds because proton loss from the diazonium intermediate is facilitated by the presence
of two electron!withdrawing groups[
Diazo Compounds 358
NH2 Cl– N2+ N2
N NaNO2, HCl N H2O N O
N N N
Scheme 48
Scheme 49
O O H O
N H2NNHPh N N –PhNH2 N2
OH N Ph
–H2O H
O O O O O O
(43)
Scheme 50
CO2Et CO2Et OR
CO2Et
NaNO2, AcOH (aq.)
H
O O O
CO2H 5 to 10 °C
N N2
O O OH
O
(44) (45) a; R = H
b; R = OAc
Scheme 51
O
O
Ar deactivated HgO O
oxidation Ar
Ar Ar Ar
N Ar
NH2 O
(46) Ar = p-MeC6H4 (48)
O
Ar
Ar
N2
(47)
Scheme 52
Some less widely used dehydrogenation reagents can be used to dehydrogenate monohydrazones
of a!diketones[ For example\ 1!diazo!0\1!diphenyl!0!ethanone has been prepared in very high
yield by treatment of benzil monohydrazone with copper"II# chloride and pyridine ð62TL3462Ł[
Dehydrogenation of monohydrazones of a!diketones has also been accomplished using calcium
hypochlorite in methanol ð50JOC1506Ł[
Oxidation of monosemicarbazones of a!dicarbonyl compounds with lead"IV# acetate is also a
useful method of preparing a!diazo carbonyl compounds\ and proceeds in a similar fashion to the
oxidation reactions discussed above ð67S424Ł[
Ph Ph Ph Ph Ph Ph
Ar TsNHNH2, C6H6 Ar H3O+
O N O N O O
N N2 N2
Ar
(49) (50) (51)
Scheme 53
The BamfordÐStevens reaction is also useful for the preparation of a!diazoacetates of unsaturated
alcohols[ For example\ acylation of "E#!but!1!en!0!ol with tosyl hydrazonoacetyl chloride gives the
ester "41#\ which upon treatment with triethylamine in dichloromethane a}ords the a!diazoacetate
Diazo Compounds 360
"42# "Scheme 43# ð57JOC42Ł[ The transformation may also be achieved in a one!pot fashion by
performing the acylation reaction in the presence of two equivalents of base[
Ts
Ts
N N O NaHCO3 Et3N
OH + O N N O N2
H CH2Cl2 CH2Cl2
H
Cl
O O
(52) (53)
Scheme 54
The a!diazo succinate diester "44# can be prepared in good yield from methyl alkynedicarboxylate
"Scheme 44# ð64BSF136Ł[ Nucleophilic addition of tosylhydrazine to the alkyne and subsequent
isomerization a}ords the tosyl hydrazone "43#\ and the a!diazo ester "44# is then obtained by
treatment of "43# with potassium carbonate[
CO2Me
MeO2C CO2Me
TsNHNH2 K2CO3 (aq.), 80 °C MeO2C
MeO2C CO2Me H N
MONOGLYME N N2
Ts
(54) (55)
Scheme 55
O
N N2 H
H H S
R1 N S C5H5N, CHCl3, silica gel
(22)
N
O N O CO2 R2
O CO2R2 H
H
(56) a; R1 = Ph, R2 = CH2CCl3 (57) a; R2 = CH2CCl3
b; R1 = PhO, R2 = CH2Ph b; R2 = CH2Ph
O
O
EtO BaO, Ba(OH)2, MeOH
EtO (23)
N
ON N2
O
(58)
Scheme 56
A limitation of diazo transfer reactions of this type is the requirement of two electron!withdrawing
substituents to activate the methylene group[ This problem can be circumvented by temporary
activation with a formyl group\ which can be introduced by Claisen condensation and is lost during
diazo group transfer[ The reaction can be performed in a one!pot sequence by using the alkali
salt formed during Claisen condensation directly in the diazo group transfer reaction ð56TL628\
57CB1511Ł[
Deformylative diazo group transfer is very useful for the synthesis of a!diazo ketones\ a!diazo
aldehydes\ a!diazo esters and a\b!unsaturated diazo ketones ð57CB1511\ 69LA"628#063Ł\ and can pro!
ceed by two possible pathways "Scheme 46#[ In the _rst pathway "a#\ a triazoline intermediate is
formed which decomposes to give the sulfonylformamide and the a!diazo ketone product[ In the
alternative mechanism "b#\ an intermediate triazine is formed\ and loss of the formyl group occurs
by alcoholysis[ When the diazo transfer reaction of a formyl ketone is performed in dichloromethane
in the presence of triethylamine\ there is evidence that the reaction proceeds by way of a triazoline
intermediate ð56TL628\ 57CB1511Ł[ The formation of a triazoline intermediate can be a problem
during diazo group transfer to some types of a!formyl cycloalkanones\ and may lead to formation
of a b!keto amide rather than the a!diazo cycloalkanone ð56TL628\ 57CB0152Ł[
O
O
O–
–Ts(CHO)N–
R
TsN3, ROH N N N2
N Ts
O O O O (a)
base, –H+
ROH, –HCO2R
R R
– (b)
TsN3, ROH
COR
O O
N CHO –TsNH–
R
N
N– N2
Ts
Scheme 57
Other proton!activating groups can be employed to achieve temporary activation of the methylene
group during the formation of a!diazo ketones[ For example\ the benzoyl group has been used as
an activator in the synthesis of steroidal a!diazo ketones ð79TL04Ł\ and the alkoxyoxalyl group has
been used as an activator during the synthesis of a\b!unsaturated diazo ketones ð57CB1511\ 63S466Ł[
A useful new diazo group transfer method for the synthesis of a!diazo ketones has been developed[
In this procedure\ tri~uoroacetylation of a ketone enolate\ followed by treatment of the resulting
Diazo Compounds 362
b!diketone with methanesulfonyl azide in the presence of triethylamine a}ords the a!diazo ketone
"Scheme 47# ð89JOC0848Ł[ This protocol is especially useful for diazo group transfer to a\b!unsatu!
rated ketones which are poor substrates for deformylative diazo group transfer[ Yields are superior
to those obtained by deformylative diazo group transfer in many other cases[
O O O O
LiN(TMS)2, CF3CO2CH2CF3 MsN3, Et3N, MeCN (aq.), RT R2
R1 R1 CF3 R1
THF, –78 °C
R2 R2 N2
Scheme 58
Phase transfer conditions can be employed in cases where deformylative diazo group transfer
cannot be used[ Tosyl azide is usually utilized as the diazo group transfer reagent\ but azidinium
salts have also been used[ When p!carboxybenzenesulfonyl azide is used as the diazo transfer reagent\
excess azide and the product sulfonamide can be removed from the product by treatment with
aqueous base[ This can be advantageous in cases where incomplete reaction complicates puri_cation
of the a!diazo carbonyl product ð57JOC2509Ł[
In some cases it is possible to accomplish diazo group transfer from diazo compounds rather
than sulfonyl azides[ For example\ reaction of 0\0!dimethylcyclohexane!2\4!dione with ethyl diazo!
nitroacetate a}ords the product of diazo group exchange "Scheme 48# ð54LA"576#103\ 58LA"611#34Ł[
O O
CO2Et O2N
Et3N, EtOH, –H+ – H+
+ N2 CO2Et
NO2 N N
O O
O
N2 + O2N CO2Et
Scheme 59
a!Diazo ketones can be prepared by diazo group transfer from azidinium compounds to activated
substrates under acidic or neutral conditions rather than basic conditions ð50LA"536#00Ł[ This reaction
can also be accomplished under acidic or neutral conditions using azidochloromethylene!
dimethylammonium chloride ð79AG643\ 79AG"E#605Ł[
Although diazo group transfer to enamines is usually employed to prepare diazo alkanes which
do not possess adjacent carbonyl groups\ the reaction can also be used to synthesize a!diazo carbonyl
compounds\ and is especially useful for the preparation of a!diazo aldehydes[ Treatment of a formyl
enamine with tosyl azide gives the corresponding a!diazo aldehyde in good yield "Scheme 59#
ð55TL0098\ 56CC188\ 69CCC2507Ł[ Ethyl diazoacetate and various diacyldiazomethanes have been
prepared from their respective enamines in this fashion ð69LA"623#69Ł[
R2
R2
R2 R3 TsN3 R1 N R3 R3 CHO
CHO + N
N R1
R1 CHO N2
N N NTs
Ts N
Scheme 60
O
O O R2
R2 R2 R1
R1 R1
+ R2
N2 R2
R1 R1 N
N N2 R1
R2
(59) (60)
Scheme 61
O O OH
O i, base
X + X R (24)
R ii, H3O+
N2 N2
X = R, OR
O-TMS
EtO2C TMS O 18-crown-6-KCN EtO2C
+ R (25)
N2 R
N2
(61)
The acylation of diazo alkanes is probably the most important and widely used method for the
synthesis of a!diazo ketones and there are many examples "Scheme 51# ð05CB0867Ł[ This method of
preparing a!diazo ketones has become popular with the advent of protocols which minimize a!halo
ketone formation during the reaction ð04JCS0380\ 05CB0867\ 13JA1440\ 13JA1445\ 14JA0617Ł[ The reaction
is a general one\ and has been applied to the synthesis of many a!diazo carbonyl compounds
ð31OR"0#27\ B!75MI 201!90Ł[ Acyl halides and anhydrides are particularly good substrates for the
reaction\ and cyclic imide chlorides also react readily ð46JA833\ 47JCS0023Ł[ Diazomethane can also
be acylated with various vinylogous acid chlorides ð70TL330Ł[
O
O excess R2CHN2 or R2CHN2 (2 equiv.) O O
R2
R1
R1 X R2CHN2, R3N –R1CO2CH2R2 R1 O R1
N2
X = Cl, Br
Scheme 62
During the formation of a!diazo ketones by reaction of diazomethane with acid chlorides\ a large
excess of diazomethane is used to scavenge the acid evolved during the reaction and prevent
decomposition of the diazo ketone ð17JCS0209Ł[ Bases such as triethylamine can be used as acid
scavengers\ and only one equivalent of the diazomethane is required in these cases ð38JA0495\
38JA0518\ 46LA"591#088\ 66JOC2646Ł[ a!Diazo ketones can be prepared by reaction of acid chlorides
Diazo Compounds 364
with diazomethane generated in situ from an N!nitrosourethane or N!nitrosourea\ however\ this
procedure can a}ord unwanted by!products ð31OR"0#27Ł[ In certain circumstances it may be advan!
tageous to acylate trimethylsilyl diazomethane rather than diazomethane because of the relative
thermal stability and reduced toxicity of this compound ð79TL3350Ł[
Carboxylic acid anhydrides are good acylating agents for diazomethane\ and two moles of
diazomethane are consumed during the reaction "Scheme 51# ð46JOC134Ł[ Attack occurs at the more
electrophilic carbonyl group of mixed anhydrides ð69HCA0946Ł[ Symmetical anhydrides formed by
treatment of carboxylic acids with dicyclohexylcarbodiimide can be used directly in the reaction
without further puri_cation ð69HCA0946\ 60LA"636#10Ł[ The disadvantage of this technique is that half
of the original acid is converted to the methyl ester rather than the diazo ketone[
a!Diazo b!dicarbonyl compounds can be prepared by acylation of a!diazo carbonyl compounds\
usually a!diazo esters\ with acid chlorides "Scheme 52#[ Another method of acylation which has a
broad scope is the reaction of diazomethyl carbonyl compounds with acyl isocyanates to give the
corresponding a!diazo b!dicarbonyl compounds "Scheme 52# ð62CB0385\ 62T0872Ł[ Some acyl ketenes
will react with diazo ketones in an analogous fashion ð67ZOR1123Ł[
O O O O O O
R2COCl R2CONCO
R1 R2 R1 R1 N R2
H
N2 N2 N2
ArCOCHCO
O O O
R1 Ar
N2
Scheme 63
Diazo acetates are less prone to undergo cycloaddition to electron!de_cient alkenes than diazo!
methane\ and react with a\b!unsaturated acyl chlorides to give the corresponding unsaturated a!
diazo b!dicarbonyl compounds ð05CB0867Ł[ However cycloaddition is problematic when additional
electron!withdrawing groups are present in the a\b!unsaturated acyl chloride ð53LA"564#36Ł[ The
ratio of reactants may in~uence the outcome of this reaction\ and an excess of diazo substrate can
lead to acylation and cycloaddition ð56CJC0616Ł[
a!Diazo b!dicarbonyl compounds can be converted into a!diazo carbonyl compounds by alkaline
cleavage "Scheme 53# ð01LA"283#12\ 05CB0867Ł[ For example\ t!butyl diazoacetate can be prepared in
good yield by treatment of t!butyl diazoacetoacetate with sodium methoxide in methanol
ð57OS"37#25Ł[ The same compound is formed when t!butyl acetoacetate is reacted with tosylazide in
aqueous acetonitrile in the presence of potassium hydroxide ð58OPP88Ł[ In this case\ isolation of t!
butyl diazoacetoacetate is not required\ and high yields are obtained if this reaction is performed in
a two!phase system in the presence of a phase transfer catalyst ð63S236Ł[ Diazophenylmethane can
be prepared from azibenzil by a reaction which is analogous to those described above ð47JOC648Ł[
O O i, NaOH (aq.) O O O
ii, H3O+ NaOMe, MeOH
R R –RCO2H X X R
–RCO2Me
N2 X=R N2 X = OR N2
Scheme 64
a!Diazo carbonyl compounds can sometimes be prepared from other a!diazo carbonyl compounds
by substitution reactions[ For example\ diazoacetic acid can be converted to diazoacetyl chloride
by treatment with the a!chloroenamine "51# "Scheme 54# ð68CC0079Ł[ Diazoacetyl chloride can then
be converted to a variety of a!diazo esters and amides with preservation of the diazo group ð68AG0901\
68AG"E#836Ł[
a!Diazo esters can be converted into the corresponding a!diazo amides by substitution with
ammonia or amines\ and this reaction can be used to prepare a!diazo acetamide from methyl
365 Hydrazones and Other 1NN Derivatives
+ O
CO2H Cl NMe2 O NMe2
+ N2 + Me2CHCONMe2
Cl
N2 Cl– O N2
(62)
Scheme 65
Scheme 66
Alkynes possessing electron!withdrawing groups do not react with cyanogen azide\ but react with
trimethylsilyl azide to a}ord triazoles which can be converted into a!diazo N!cyano imines by
deprotonation and subsequent reaction with cyanogen bromide "Scheme 56# ð70BSB504Ł[
i, TMS-N3 Y R Y R Y R
ii, H2O BrCN
Y R
iii, NaH, THF N – N –NaBr N N
CN N2 N CN
N N
Na +
Y = electron-withdrawing group
Scheme 67
a!Diazo imines can be synthesized by the reaction of acyl phosphoranes with azides "Scheme 57#[
Treatment of cyanogen azide with an acyl phosphorane results in formation of the triazoline which
eliminates a phosphine oxide to form the triazole "54# ð55JOC0476\ 69TL4114Ł\ which then undergoes
ring opening to a}ord the a!diazo imine ð79TL898\ 70AG007\ 70AG"E#002\ 70BSB504Ł[
+
O R1 R2
Ph3P O– R1 R
R2 NCN3 –Ph3PO
R1 R2
R1
N N N2 N CN
PPh3 N N N CN
N CN
(65)
Scheme 68
Diazo Compounds 366
2[01[2[3[1 a!Diazo amidines and imidates
The most general method of preparing a!diazo amidines is by diazo group transfer to ynamines[
Ynamines function as acceptors in diazo group transfer reactions and undergo sequential ð1¦2Ł!
addition and ring opening with various azides "Scheme 58# ð70ZN"B#107Ł[ In principle\ diazo amidines
can be in equilibrium with the corresponding triazoles[ However\ in cases where the imine substituent
is a good electron!acceptor group\ the open chain compound predominates ð61CB1852\ 68LA0717Ł[ In
cases where the azide substituent is a weak electron!acceptor or an electron!donor\ the triazole is
favoured ð55JOC0476\ 62LA0494Ł[ The presence of bulky N!substituents or electron!acceptor groups
on the ynamine tends to favour formation of the open chain products ð61S460\ 63CB1402Ł[
R1 NR22 R1 NR22
R1 NR22 + N3 Y
N N N2 N Y
N Y
(65)
Y = electron-withdrawing group
Scheme 69
a!Diazo imidates\ such as "55#\ can be prepared by reaction of alkynyl ethers with azides "Scheme
69# ð52TL0728\ 54CB512\ 61CB1864\ 70BSB504\ 71S038Ł[ In contrast to the alkynyl amines\ the reaction
between alkynyl ethers and 3!dimethylaminobenzene sulfonyl azide occurs without isolation of the
presumed intermediate triazoles[ However\ addition of sulfonyl azides to substituted alkynyl ethers
results in an equilibrium between the triazoles and their corresponding a!diazo imidates ð61CB1864\
62LA0494Ł[
R1 OR2 R1 OR2
R1 OR2 + N3 R3
N N N2 N R3
N R3
(66)
Scheme 70
S S
Y CN
N3 ROH (aq.) NH2
Y CN + + (27)
N + BF4– N + BF4–
N2
Et Et
Y = COR, CO2R, CONH2, SO2R, Ar
There are several methods for the preparation of a!diazo nitriles which do not rely on diazo group
transfer reactions[ For example\ the explosive compound dicyano diazomethane can be obtained
by oxidation of the corresponding hydrazone with lead tetraacetate ð54JOC3087Ł\ and ethyl cyano!
diazoacetate has been prepared in quantitative yield by thermal fragmentation of the a!diazo
thiatriazole "56# "Equation "17## ð71TL0092Ł[
367 Hydrazones and Other 1NN Derivatives
N N
N CHCl3, 60 °C EtO2C CN
EtO2C (28)
S
N2
N2
(67)
The cycloaddition reaction of acrylonitrile with phenylazide produces the triazoline "57#\ which
can be converted into the a!diazo nitrile "58# by treatment with triethylamine in benzene "Scheme
60# ð55CB364Ł[ However\ only an equilibrium mixture of "57# and "58# is obtained by this method[
NC NC
PhN3
NC
N N N2 NHPh
N Ph
(68) (69)
Scheme 71
Scheme 72
Scheme 73
Diazo group transfer reactions can also be used to prepare a!diazo sul_nyl compounds[ An
additional electron!withdrawing group is required in the sulfoxide precursor to facilitate the reaction[
For example\ the diazo cephem "62# can be prepared directly by diazo group transfer because
a vinylogous carbonyl group is present in the precursor "Equation "18## ð65CC427\ 66JCS"P0#1187\
68JOC3586Ł[
O O
H H H H
S S N2
R1 R43N, MeCN or CH2Cl2 R1
(29)
N N
O R3 O R3
CO2R2 CO2R2
(73)
Deformylative diazo group transfer provides an indirect route to a!diazo sulfonyl compounds
which do not possess additional electron!withdrawing groups\ and compounds such as a!phenyl"p!
toluenesulfonyl#diazomethane and t!butylsulfonyldiazomethane have been prepared using this
approach ð62TL4196\ 64T486Ł[
Diazo vinyl sulfones can be synthesized by reaction of diazo alkanes with thiiriene!0\0!dioxides
"Scheme 63#[ However\ formation of the diazo compound "63# is always accompanied by a signi_cant
amount of pyrazole formation ð60JA365\ 79CB0521Ł\ and when the reaction is performed with diazo!
methane\ the product reacts further to give a pyrazoline ð79CB0521Ł[
N R2 O O R1 R1
R1 R1 N
R1 S R1
+ R2 CHN2 +
S R1 R1 N
S N2 N R2
O O R2
O O H
(74)
Scheme 74
Diazo substitution provides an alternative to diazo group transfer for the preparation of sulfur!
substituted diazo compounds[ Although sulfonyl chlorides are generally not electrophilic enough
to react with diazo alkanes ð22CB0901Ł\ there are some exceptions[ For example\ diazophenylmethane
will react with tosyl chloride to give diazophenyltosylmethane ð62C219Ł\ and phenylsul_nyl diazo!
methane can be prepared by treatment of diazomethane with phenylsul_nyl chloride[
Scheme 75
O O
NaNO2, AcOH
P NH2 P N2 (31)
R1 R1
R2 R2
R1, R2 = OMe, Ph
Diazo transfer is an important method for the synthesis of a!diazo phosphoryl compounds
which possess electron!withdrawing groups "Equation "21##[ Several a!diazo phosphine oxides\
phosphonates and phosphinates have been prepared by this method ð64AG148\ 64AG"E#111Ł[
Thiophosphoryl diazo alkanes have also been synthesized by diazo group transfer ð68T070\ 68TL1304Ł[
Diazo Compounds 370
In some cases\ azide transfer competes with diazo group transfer and thiophosphoryl azides may
be isolated instead of the required diazo compounds ð68T070Ł[
O O
base, TosN3, solvent P X
P X R1 (32)
R1
R2 R2
N2
Deformylative diazo group transfer is of limited use for the synthesis of diazo phosphoryl
compounds[ For example\ deprotonation of diethyl "1!oxoethyl# phosphonate followed by reaction
with tosyl azide a}ords only a low yield of diethyl "diazomethyl#phosphonate ð48CB0234\
58LA"629#083Ł[ The major products of these reactions are triazoles such as "66# "Scheme 66#[
O
P R2 –
R1 + OHC NTs
O O O– R1
R2 N2
P CHO P
R1 R1
R1 N Tos
R1 N N
R2 O R2
P +
R1 O– N NH
R1 N
(77)
R1 = OEt, Ph; R2 = H, OEt, Ph
Scheme 77
R2 R3
R5 R2 R3
R1 POR42 R5 R6 Et2O, 0 °C R1 POR4 2 heat or hν POR42
+ R6
R5
N2 N
R2 R3 R1 N2
N
R6
Scheme 78
R1 R2 R1 R2
PO(OR3)2
R4N3 PO(OR3)2 silica gel, H2O PO(OR3)2
R1 R2 N N2 O N2
R4
Scheme 79
+ O
Ph3P O– +
TsN3 Ph3P –
Ph3P • • O NTs
N N
N Ts N2
(78)
Scheme 80
Scheme 81
Scheme 82
O O O O
Hg THF, 20 °C Et3SiHg –Hg Et3Si
(Et3Si)2Hg + R R R R
N2 N2 N2 N2
R = Me, OMe
Scheme 83
Me Me
EtO2C Hg CO2Et Me Me
Si S TMS Si CO2Et
+ TMS S Si TMS (33)
N2 N2 Me
Me N2
(79) (80)
There are many methods other than substitution of diazo alkanes which can be used to prepare
silicon!substituted diazo alkanes[ For example\ triphenylsilylphenyldiazomethane has been prepared
by the oxidation of the corresponding hydrazone with manganese"IV# oxide ð57TL3862Ł[ The Bam!
fordÐStevens reaction of trialkylsilyl!substituted hydrazones has also been used to prepare silicon!
substituted diazo alkanes ð58CJC3242\ 67JA883Ł[
Trimethylsilyldiazomethane can be synthesized in reasonable yield by treatment of N!"trimethyl!
silyl#methyl!N!nitrosourea with potassium hydroxide "Scheme 73# ð57JA0979\ 61JOM"33#168\
62JCS"D#372Ł[ Treatment of lithiated trimethylsilylmethane with tosyl azide at 9>C a}ords the same
compound in modest yield\ and this method can be employed to prepare bis"trimethyl!
silyl#diazomethane ð79JA0473Ł[ Bis"trimethylsilyl#diazomethane can be prepared by diazo group
transfer of trimethylsilyl azide to the silaethene "70# via the triazasilacyclopentene "71# "Scheme 74#
ð70CB2407Ł[
Scheme 84
There are many examples of the synthesis of germyl!substituted diazo compounds[ Diazomethane
and diazoacetates can be metallated directly using dimethylaminotrimethylgermane "Scheme 75#
ð69JCS"A#1843\ 60JOM"16#292\ 66JOM"016#08Ł\ and bis"trimethylgermyl#diazomethane can be prepared
analogously[ Trimethylgermyltrimethylsilyl diazomethane has been prepared from trimethyl!
silyldiazomethyl lithium ð79JOM"080#260Ł\ and this compound and bis"trimethylgermyl# diazo!
methane have been synthesized by diazo group transfer "Equation "23## ð79JA0473Ł[
373 Hydrazones and Other 1NN Derivatives
Me TMS
TMS Et2O, –10 °C TMS TMS
Me Si TMS
Me2Si + TMS N3
TMS N N N2
TMS N
(81) (82)
Scheme 85
Scheme 86
Scheme 87
O O
Et2O, –30 °C to 20 °C Me3Pb
Me3PbN(TMS)2 + R R (36)
N2 N2
R = Me, Ph, OEt
Diazo Compounds 374
2[01[2[4[6 Diazo alkanes substituted with boron or thallium
The _rst boron!substituted diazo alkane to be prepared was ethyl "0\1\2!benzodioxaborol!
1!yl#diazoacetate "72#\ which was prepared by reaction of 1!chloro!0\1\2!benzodioxaborole and
lithium or mercury "ethyl diazoacetate# "Scheme 77# ð63LA0656Ł[ Two other examples of diazoalkyl
boranes are known ð78CB484\ 80JA4745Ł[ For example\ ðbis"diisopropylamino#boranylŁdiazomethane
was isolated after treatment of an ethereal solution of lithiated diazomethane with bis"diiso!
propylamino#chloroborane at low temperature "Equation "26##[
O O
EtO2C Hg CO2Et B Cl O CO 2Et B Cl Li CO2Et
O O
B
N2 N2 CH2Cl2, –10 °C to 0 °C C5H12, THF, Et2O, –100 °C N2
O N2
(83)
Scheme 88
Pri2N Pri2N
N2 Et2O, –78 °C
B Cl + B (37)
Li
Pri2N Pri2N N2
Pri2N Pri2N +
N2
PhMe, RT
Cl P • N2 + BY3 Cl P (38)
Pri2N Pri2N BY3–
BY3 = BF3•OEt2, BH3•THF
There are few examples of thallium!substituted diazo compounds\ but diazo bis"dimethyl!
thallium#methane can be prepared by treatment of diazomethane with either the metallated amine
"73# or trimethylthallium "Scheme 78# ð65JOM"019#020Ł[
Scheme 89
RLi or N2 MeLi
H2C N2 N2O
TMS(Me)NLi Li
Scheme 90
375 Hydrazones and Other 1NN Derivatives
Metallation of ethyl diazoacetate can be accomplished by reaction with butyl lithium at low
temperature in an ethereal solvent "Scheme 80# ð69AG180\ 69AG"E#290Ł[ The reagent can be prepared
by transmetallation from mercury bis"ethyl diazoacetate# "see Section 2[01[2[4[01# using phenyl or
butyl lithium\ or lithium thiolates[
O O O O
BuLi, –100 °C RLi or RSLi Hg
Li
OEt OEt EtO OEt
–70 °C
N2 N2 N2 N2
Scheme 91
Scheme 92
PPh3 PPh3
Cl NO Cl NO
I2
Os CO2Et Os CO2Et
Hg I
I Ph P Ph3P
3 N2 N2
(87)
Scheme 93
TMS N2
I PMe3
Rh
Me3P Me
PMe3
(88)
R2 PR13
C6H6
(PR13)PdX2 + Hg[C(N2)R2]2 Pd X (39)
N2 PR1 3
(89)
R2 PR13 N2
THF C6H6
(PR13)PdX2 + LiC(N2 )R2 Pd (PR13)4Pd + Hg[C(N2)R2]2
N2 2
PR13 R
(90)
R1 = Et, Bu, Ph; R2 = CO2Et, C(O)Me, Ph, p-MeC6H4, Pri, But; X = Cl, Br, I
Scheme 94
Et2O Ag Ag
2MeCO2Ag + 3 H2C N2 • + 2MeCO2Me + 2N2 (41)
pyridine N2 N
Scheme 95
Mercury may be introduced directly into diazomethyl compounds which possess an electron!
withdrawing group on the diazo carbon ð0784CB104Ł[ This transformation is usually accomplished
by treatment of the diazo compound with mercury"I# oxide in the presence of a water!absorbing
agent[
Mercury bis"ethyl diazoacetate# can be prepared in high yield by treatment of ethyl diazoacetate
with mercury bisðbis"trimethylsilyl#amideŁ at −19>C in diethyl ether ð60JOM"16#292Ł[
Bis"diazomethyl# mercury is a highly explosive compound\ and has been prepared by reaction of
mercury"II# acetate with diazomethane "Scheme 85# ð52NAT892Ł[ This compound has also been
prepared by lithiumÐmercury exchange from diazomethyl lithium with mercury"II# chloride
ð57TL4126Ł[ Alkyl! and arylmercury diazo alkanes can be prepared in good yield by metallation
of diazo alkanes with alkylmercury bis"trimethylsilyl#amides or by reaction of diazo alkanes with
alkyl! or arylmercury ethoxides "Scheme 86# ð60JOM"16#292\ 62JOM"43#12Ł[
H2C N2 + Hg[N(TMS)2]2 Hg(H2C N2)2 H2C N2 + Hg(OAc)2
Scheme 96
TMS R1 HgR2
R1HC N2 + R2Hg N R1HC N2 + R2HgOEt
TMS N2
Scheme 97
R R
O base R R
N O • R R
NO N2
R R
(92)
Scheme 99
The diazoallene "83# has been implicated as an intermediate during the base!catalysed decompo!
sition of the bis"N!nitrosourethane#cyclopropane "82# "Scheme 099# ð60TL206\ 61JOC582Ł[ The prod!
uct isolated from this reaction was that produced by trapping of the carbene derived from "83# with
1\2!dimethylbut!1!ene[
NO
N ON
Ph Ph
CO2Et MeONa Ph N CO2Et MeONa
• • N2
Ph CO2Et •
N Ph
Ph
NO
(93) (94)
Scheme 100
Diazoketene "84# has been prepared by treatment of diazoacetyl chloride with 0\3!diazabicyclo!
ð1[1[1Łoctane "dabco# "Equation "31## ð68AG0901\ 68AG"E#836Ł[
O
dabco, Et2O, heat
O • • N2 (42)
Cl N2 (95)
A variety of diazo cycloalkenes can be prepared by diazo transfer[ For example\ 4!diazo!0\1\2\3!
tetraphenylcyclopentadiene can be synthesized in high yield by treatment of the 0\1\2\3!tetra!
phenylcyclopentadiene with p!toluenesulfonyl azide and triethylamine in dichloromethane
ð79TL898Ł[
o! and p!Quinone diazides are synthesized in good yield by diazotization of amino phenols[
Although the intermediate diazonium salts may be isolated in some cases\ they are readily depro!
tonated in acidic media[ Deprotonation can also be accomplished with a mild base ð34JA844\
54LA"570#34\ 60S370Ł[
The conjugated diazo allene "87# has been implicated as an intermediate during the ~ash vacuum
pyrolysis of the heterocyclic compound "86# "Scheme 091# ð79JOC3954Ł[ The compound actually
isolated from the reaction was the enyne "099#\ produced by ring opening of the carbene!derived
methylenecyclopropene "88#[
N2
N N
Ph Ph
Ph O O • Ph
(97) (98) (99) (100)
Scheme 102
Copyright # 1995, Elsevier Ltd. All R ights Reserved Comprehensive Organic Functional Group Transformations
3.13
Synthesis of P, As, Sb and Bi
Ylides (R3P1CR2, etc.)
ÉAMONN J. COYNE and DECLAN G. GILHEANY
University College Dublin, Republic of Ireland
2[02[0 PHOSPHONIUM YLIDES FROM PHOSPHONIUM SALTS 381
2[02[0[0 Preparations of Phosphonium Salts 381
2[02[0[1 Deprotonations of Phosphonium Salts 382
2[02[0[2 Dehalo`enations of Phosphonium Salts 384
2[02[0[3 Desilylations of Phosphonium Salts 385
2[02[0[4 Ylides from Vinylphosphonium Salts 385
2[02[0[5 Ylides from Cyclopropylphosphonium Salts 385
2[02[0[6 Ylides by the Electrolysis of Phosphonium Salts 386
2[02[1 PHOSPHONIUM YLIDES FROM PHOSPHINES 386
2[02[1[0 Reactions with Carbenes 386
2[02[1[1 Via Azines 386
2[02[1[2 Reactions with Activated Multiple Bonds 387
2[02[1[3 Reactions with Aziridines 387
2[02[1[4 Reactions with Arynes 387
2[02[2 PHOSPHONIUM YLIDES FROM PHOSPHORANES 388
2[02[3 PHOSPHONIUM YLIDES FROM OTHER PHOSPHONIUM YLIDES 388
2[02[3[0 By Halo`enations 388
2[02[3[1 By Alkylations and Acylations 388
2[02[4 PREPARATION OF As\ Sb AND Bi YLIDES 499
2[02[4[0 From the Precursor Onium Salts 499
2[02[4[1 From Arsines\ Stibines and Bismuthines 499
2[02[4[2 From the Dihalo Pentacoordinate Derivatives 499
2[02[4[3 From the Tertiary Oxides 499
There are a great many more preparations of the phosphonium ylides than of their group 04
analogues and this is re~ected in this review[ Thus 2[02[0Ð2[02[3 are concerned with the preparation
of phosphorus ylides and 2[02[4 deals with the other ylides\ classi_ed in a similar manner[
There is a good variety of methods available for the construction of the P1C bond[ However\
by far the most commonly used method for the synthesis of phosphonium ylides is by deprotonation
of an appropriate precursor phosphonium salt*the {salt method|[ Therefore this method is discussed
_rst\ including reference to methods for obtaining the requisite phosphonium salts\ followed by the
related dehalogenation and desilylation of phosphonium salts[ Thereafter\ all the other preparatively
useful methods are discussed\ grouped according to the source of the phosphorus atom viz[ phos!
phonium salts\ phosphines and phosphoranes[ Finally\ although they are not strictly methods for
construction of the P1C bond\ the most common interconversions of ylides are brie~y described[
Phosphorus ylides have been comprehensively reviewed by Johnson ðB!82MI 202!90Ł\ and the older
compilation of methods for the Wittig reaction by Gosney and Rowley is still very useful ðB!68MI
380
381 P\ As\ Sb and Bi Ylides
202!90Ł[Sections on ylides can also be found in other series ðB!68MI 202!91\ 80COSŁ although mention
of arsenic\ antimony and bismuth ylides is brief at most[ However\ these ylides have been reviewed
"with particular attention to arsenic# by Lloyd\ Gosney and Ormiston ð76CSR34Ł[
R2 R2 R2
+ –H+
PR13 + X R13P X– R13P
R3 R3 R3
Scheme 1
ðB!89MI 202!90Ł[ The preparation of phosphonium salts has been comprehensively reviewed by
Cristau and Plenat ðB!83MI 202!90Ł[
Br Ph3P +
PPh3 Br– (1)
F3C
F3C
complexed ylides "20P ¼ 11 ppm^ JP!C ¼ 49Ð54 Hz# ð65JOC0057Ł[ The earliest procedure for salt!free
ylide solutions\ due to Bestmann and Arnason ð51CB0402Ł used sodium amide in liquid ammonia to
deprotonate the salt\ followed by addition of benzene\ ammonia evaporation and airless _ltration
of the insoluble Na¦ salts[ Later THF replaced benzene but more recently the need for liquid ammonia
has been circumvented by use of NaH in THF ð69LA"628#100Ł or sodium hexamethyldisilazide "Na!
HMDS# in a variety of solvents ð65CB0583\ 75CB0249Ł\ again with _ltration of the insoluble sodium salts[
Other complications which attend the deprotonation of phosphonium salts include ligand ex!
change and elimination[ It is known ð53JOM"1#090\ 54JA2356\ 55AG"E#857Ł that treatment of phos!
phonium salts with carbanionic reagents can result in a ligand exchange process via a pentavalent
intermediate "Scheme 1#[ This process is favoured where RPh and has in fact been used as a route
to ylides\ for example the cyclopropylide in Scheme 2 ð56CC299Ł[ b!Elimination must be taken into
account when there is a potential leaving group at the b!position or another acidic hydrogen[ Thus
b!bromoethyltriphenylphosphonium bromide and b!triphenylphosphonioethyltriphenylphos!
phonium bromide undergo initial elimination of hydrogen bromide and triphenylphosphine\ respec!
tively\ when treated with phenyllithium ð55JOM"5#194Ł[
R1
+ R2Li R1 +
R14 PX– R2 P R13PR2 Br– + R1Li
R1
R1
Scheme 2
+
Ph4PBr– + –C6H6
Li PPh3 Br– PPh3
–LiBr
+
PhLi
Scheme 3
From Phosphonium Salts 384
2[02[0[2 Dehalogenations of Phosphonium Salts
Ylides may be derived from phosphonium salts by abstraction of an a!halogen rather than an
a!H[ This can be a problem when both are present\ but it can be controlled by variation of the
halide and the base[ This is shown in Table 2 where it can be seen that a!halogen attack increases
Cl×Br×I and BunLi×PhLi×Li piperidide×HMDS[ Abstraction of halogen is also a useful
route to otherwise inaccessible ylides and thence to alkenes[ Thus Smithers ð67JOC1722Ł was able to
prepare terminal vinyl bromides by the route shown in Scheme 3[
Br R1 R1
R1Br + BuLi
Ph3P Ph3P Br Br–
Br Br R2CHO R2 Br
Scheme 4
The system resulting from the addition of triphenylphosphine to tetrahalomethanes is also quite
useful for the production of haloylides[ This complex reaction system is summarised in Scheme 4[
With careful control of conditions it is possible to select each of the di}erent possible pathways[
Thus the addition of controlled amounts of water gives the dichloro and monochloro salts
ð64AG"E#790\ 66S568\ B!68MI 202!92Ł\ and the system is a well!known reagent for the conversion of
alcohols to halides ðB!68MI 202!92Ł[ Also the dichloro ylide "0# has been used for the preparation of
a wide variety of dichlorovinyl systems ð60JOC2275\ 65BSF1957\ 77TL2992\ 80SL472Ł[ Vorbruggen et al[
ð89T2378Ł cleverly combined these aspects of the system\ _rst converting a carboxylic acid into the
chloride which subsequently acylated the ylide "0#[ The dibromo derivative is easier to generate
and use ð51JA0634\ 61TL2658\ 67JOC1722\ 89S774Ł\ but the di~uoro case ð62JA7356\ 89T4102Ł is more
complicated[ This is because\ on generation\ in the absence of other reactants\ it dissociates giving
di~uorocarbene which in turn can be trapped by more nucleophilic phosphines ð72JOC2505Ł "see
2[02[1#[ The monochloro! and mono~uoromethylides can also be prepared using this sort of system
with iodochloromethane ð68BCJ0086Ł and iodo~uoromethane ð64JOC1685Ł respectively\ as the elec!
trophiles[ Fluorine!containing ylides have also been reviewed ð70RCR179\ 71RCR0Ł[
Cl– Cl–
+
Cl
PPh3 (1) + +
Ph3P + CCl4 Ph3PCCl3 Cl– Ph3P + Ph3PCl2 Ph3P PPh3
Cl
Cl Cl
(1)
Ph3P H2O
Cl
+ +
Ph3P + Ph3P Cl
Cl
Scheme 5
385 P\ As\ Sb and Bi Ylides
2[02[0[3 Desilylations of Phosphonium Salts
This is another alternative to deprotonation and is the best way of making truly salt!free non!
stabilised ylides[ Usually it is the trimethylsilyl group which is removed\ for example\ meth!
ylenetrimethyphosphorane was _rst made by the route shown in Scheme 5 ð57CB484Ł[ A shorter
modern version of this route uses the nonnucleophilic tri~ate anion as shown in Scheme 6\ but is
only applicable to methylides ð68JA5341\ 75CRV830Ł[
+ –RO-TMS
TMS PMe3 –OR Me3P CH2
Scheme 6
Ph3P +
CsF
TMS OTf TMS PPh3 Ph3P CH2
–TMS-F
Scheme 7
+ NUC (2)
NUC – PPh3 PPh3
CHO +
CHO
–Ph3PO
+ PPh3
PPh3 62%
O– O O
Scheme 8
CO2Et RCO2–
RCO2 CO2Et (4)
+
PPh3 Ph3P
Scheme 9
X X O X
C6H6
PhHg Y + Ph3P Ph3P
∆ –Ph3PO
Br Y Y
Scheme 10
SEt NaH
SEt
TsNHN Ph3P (5)
SEt Ph3P SEt
EPh PhLi
EPh
PhE Ph3P (6)
EPh Ph3P EPh
Scheme 11
O O
O OSiMe2But O
Ph3P/THF i, BuLi
(CH2)n TfOSiMe2But (CH2)n + ii, RCHO (CH2)n R
PPh3 iii, HF
Scheme 12
These reactions have the drawback that they may turn out to be rather complex when examined
in detail[ An example of this would be the addition of phosphines to acrylonitrile where very careful
control of conditions and addition of an agent to promote proton transfer are necessary ð51JA378\
53TL0542\ 54JOC0246\ 56TL1390\ 57BCJ1704\ 69JOC2934\ 73SC0156\ 77T3542\ 78TL1620Ł[
The reactions of phosphines with activated alkynes are not as useful because the reactions tend
to be very complicated[ A case in point is the reaction with dimethyl acetylenedicarboxylate "DMAD#
which with careful control yields a bis!ylide "Equation "7## ð56JCS"C#1331Ł but which can also yield
several other products ð50JCS1015\ 54CB252\ 56JCS"C#1331\ 58JCS"C#0099\ 78JCS"P0#1314Ł[ Dibenzoyl!
acetylene reacts similarly ð69JCS"C#4Ł[
Ph3P PPh3
PPh3
MeO2C CO2Me (8)
MeO2C CO2Me
Scheme 13
X
Et3N
Ph3PCl2 + X Y Ph3P (10)
Y
2[02[3[0 By Halogenations
A variety of halogenating agents will convert an ylide bearing an a!H to the halo!substituted
derivative ðB!82MI 202!93Ł[ This is the preferred route to a!halo ylides because the alternative salt
method is complicated by the possibility of base attack at the halogen "see 2[02[0[2#[ In the absence
of any other reagent the maximum yield of ylide is 49) with the other 49) being the conjugate
acid of the original ylide\ because the initial product is the a!halophosphonium salt which undergoes
transylidation ð50CB1885Ł "Scheme 03#[ However\ there are several ways to raise the theoretical yield
to 099)] use of excess halogen ð51JOC887\ 52JOC354Ł^ use of added base\ e[g[\ pyridine or triethylamine
ð51JOC887Ł^ use of t!butylhypohalite as halogenating agent*the t!butoxide generated acts as the
base ð51JOC887Ł[
X Ph3P X
X2 + R +
Ph3P R Ph3P X– Ph3P + Ph3P R
R R
Scheme 14
Acylation of ylides is similar and has been studied in as great detail ðB!82MI202!93Ł[ The acylating
agent of choice is the acyl halide or acyclic acid anhydride[ Acylation is particularly useful for the
preparation of b!keto ylides which are not reliably available by quaternisation of a!bromoketones
"see 2[02[0[0#[ Once again the reaction is invariably complicated by transylidation e}ects because of
the extra carbanion stabilising e}ect of the added acyl group\ and again various strategies have been
devised to overcome the resulting loss of yield ðB!82MI 202!93Ł[
499 P\ As\ Sb and Bi Ylides
2[02[4 PREPARATION OF As\ Sb AND Bi YLIDES
Methods used for the preparation of As\ Sb and Bi ylides are in general similar to those used for
phosphorus ylide generation[ Perhaps a di}erence could be noted in the shift of emphasis away
from the salt method towards the carbene method[
Copyright # 1995, Elsevier Ltd. All R ights Reserved Comprehensive Organic Functional Group Transformations
3.14
Doubly Bonded Metalloid
Functions (Si, Ge, B)
TAO YE and M. ANTHONY McKERVEY
The Queen’s University of Belfast, UK
2[03[0 GENERAL METHODS FOR THE PREPARATION OF C1METALLOID
FUNCTIONS "Si\ Ge\ B# 490
2[03[0[0 Doubly!bonded Silicon Functions 490
2[03[0[1 Doubly!bonded Germanium Functions 492
2[03[0[2 Doubly!bonded Boron Functions 493
R1 R3 R1 R3 R2
Si Ge R1 B
R4 R4 R3
R2 R2
(1) (2) (3)
Several routes leading to the formation of C1metalloid functions "Si\ Ge\ B# have been exploited[
The principal methods may be assigned to one of three general categories] "i# photochemical
generation\ "ii# generation by pyrolysis and "iii# processes involving 0\1!elimination reactions[
490
491 Doubly Bonded Metalloids "Si\ Ge\ B#
generation of silenes ð76OM0395Ł[ In addition\ photochemical methods for the generation of silenes
"4# from the silacyclobutanes "3# are also possible ð68JA1380\ 70T1764Ł[ The silene ""4#\ R0 R1 Me#
has been detected by IR spectroscopy of products trapped by the matrix!isolation technique
ð74CRV308Ł[ Silenes "6# and "8# can be prepared via ð1¦3Ł cycloreversion processes from pyrolysis
of silabicycloð1[1[1Łoctadiene derivatives "5# and "7# "Scheme 0# ð71OM109\ 71JA5039\ 79JA3869\
72JA5614Ł[ Two indirect routes to silenes\ one derived from silylenes and the other from silylcarbenes\
are of some generality and importance ð75AOC"14#0Ł[ Photolytic decomposition of trimethyl!
silydiazomethane "09# yields a!silylcarbenes which then smoothly rearrange to give 0\0\1!trimethyl!
silaethylene "00# "Equation "1## ð65JA6733\ 65JA6735Ł[ 0!Methylsilene "03# can be produced from
photoconversion of dimethylsilylene "02# and is stable for many hours in argon at 24 K[ Dimethyl!
silylene "02# can be obtained\ in turn\ by irradiation of dodecamethylcyclohexasilane "01# "Scheme
1# ð70JA0734\ 72JA5065\ 73JA414Ł[ Similarly\ irradiation of the cyclic divinyldisilane "04# yields the
cyclic silene "05# "Equation "2## ð80JA2875Ł[ Alternative routes to the formation of silenes involve
0\1!elimination reactions[ Thus addition of t!butyllithium to vinyl chlorosilanes "06# produces silenes
"07# by 0\1!elimination of lithium chloride "Equation "3## ð79JA3869\ 80AG"E#333\ 80OM1418Ł[ In 0881
Apeloig and co!workers reported a new route for silene formation which involves a Peterson!type
elimination process[ One example is shown in Equation "4# ð81OM1215Ł[
R2 R1
400–700 °C
R1 Si (1)
Si
5–100%
R2
(4) (5)
Me
R
Si
Me
∆
CF3 Si
R
CF3
(6) (7)
R = H or TMS
Me
R
Si Me But
∆
But Si
R
(8) (9)
R = Me or Ph
Scheme 1
Me
TMS hν
Si (2)
N2
Me
(10) (11)
hν hν H
(Me2Si)6 (Me2Si)5 + Me2Si Si
254 nm 450 nm
Me
(12) (13) (14)
Scheme 2
C1Metalloids "Si\ Ge\ B# 492
TMS
TMS hν
Si Si Me (3)
Me
(15) (16)
R1 R1
LiBut
R2 Si Si (4)
Cl R2 But
(17) (18)
TMS
O
(TMS)3SiLi•3THF Si
TMS (5)
Et
Et
Ge Et
450 °C
CF3 Ge (6)
Et
Cl CF3
(19) (20)
Me3Ge
450 °C
N2 GeMe2 (7)
Ph Ph
(21) (22)
Ph
N2 Cu, 60 °C
Ph2Ge + Ge (8)
R
Ph R
R = Ph, CO2Et
493 Doubly Bonded Metalloids "Si\ Ge\ B#
R2 R2
ButLi, –78 °C
R1 Ge Ge (9)
–ButH, –LiX
X R1
(23) (24)
Li
F MgBr ButLi –50 °C
Ge Ge Ge But Ge
F F –78 °C F –LiF But
(25) (26)
Scheme 3
X
B
∆
CF3 X B (10)
CF3
(27) (28)
X = OMe or NMe2
C1Metalloids "Si\ Ge\ B# 494
X
N B
MNR2
N B (11)
–MX, –HNR2
(29) (30)
X = F, Cl; M = Li, Na; NR2 = N(TMS)2, N(TMS)But
Copyright # 1995, Elsevier Ltd. All R ights Reserved Comprehensive Organic Functional Group Transformations
3.15
Doubly Bonded Metal Functions
TAO YE and M. ANTHONY McKERVEY
The Queen’s University of Belfast, UK
2[04[0 INTRODUCTION 496
2[04[1 GENERAL METHODS FOR THE PREPARATION OF THE C1METAL FUNCTION 497
2[04[2 THE C1Ti FUNCTION 497
2[04[3 THE C1Zr FUNCTION 498
2[04[4 THE C1V FUNCTION 409
2[04[5 THE C1Nb FUNCTION 409
2[04[6 THE C1Ta FUNCTION 400
2[04[7 THE C1Cr FUNCTION 402
2[04[8 THE C1Mo FUNCTION 402
2[04[09 THE C1W FUNCTION 403
2[04[00 THE C1Mn FUNCTION 407
2[04[01 THE C1Fe FUNCTION 408
2[04[02 THE C1Ru FUNCTION 419
2[04[03 THE C1Rh FUNCTION 419
2[04[04 THE C1Re FUNCTION 410
2[04[05 THE C1Os FUNCTION 411
2[04[0 INTRODUCTION
These compounds\ LnM1CR0R1\ are generally named as metal carbene "alkylidene# complexes
and are often subdivided into two broad groups[ In the _rst group the ligated carbene carbon
typically possesses heteroatom substituents or aryl groups[ These carbene complexes act as carbon
electrophiles toward other chemical species and are referred to as Fischer!type carbenes[ The second
group of metal complexes are called Schrock!type carbenes or alkylidene complexes[ The ligated
carbon of this type of carbene species is attached directly to a metal by a double bond while the
other two bonds are not attached directly to any heteroatom[ In contrast to the Fischer!type
carbenes\ the Schrock!type carbene "alkylidene# complexes behave chemically as carbon nucleo!
philes[
This chapter will concentrate on the methods for the synthesis of the nonheteroatom!stabilised
carbene "alkylidene# complexes[ Methods for the preparation of heteroatom!stabilised carbene
complexes are summarised in Chapter 4[13[1[ Although some workers have preferred to use the
terms {carbene| and {alkylidene| to distinguish complexes having di}erent types of reactivity\ in this
chapter no distinction will be made between the two terms and all the nonheteroatom!stabilised
metal complexes which will be discussed are simply referred to as carbenes[
496
497 Doubly Bonded Metal Functions
2[04[1 GENERAL METHODS FOR THE PREPARATION OF THE C1METAL FUNCTION
Reviews containing information on the synthesis of nonheteroatom!stabilised carbenes have
appeared ð79MI 204!90\ B!72MI 204!90\ B!75MI 204!90\ B!77MI 204!90\ 80MI 204!90Ł[ Several routes leading
to the formation of carbene complexes have been exploited[ The principal methods may be divided
into three broad categories] "i# carbonÐmetal double bond formation via an intermolecular reaction
of a metal complex with a carbene or carbene precursor "Equation "0##^ "ii# transformation of a
molecule containing a carbonÐmetal single bond or triple bond into a metal carbene "Scheme 0#^
and "iii# modi_cation of a preformed metal carbene molecule\ that is exchange or modi_cation of
the carbene ligand\ exchange or modi_cation of the ligand"s# on the metal\ or by changing the
oxidation state of the metal "Scheme 1#[
R1 R1
MLn1 + Ln2M (1)
R2 R2
R1 R1
Ln1M Ln2M Ln1M R1
R2 R2
Scheme 1
R1
LnM Exchange or modification
R2
Exchange or modification
Scheme 2
A wide range of synthetic procedures can be used for the preparation of nonheteroatom!stabilised
carbenes and some of these have proved very successful[ However\ no general methods exist which
are suitable for preparing all types of nonheteroatom!stabilised carbenes[ In this chapter\ the general
survey of the synthetic routes leading to metal carbenes has been organized according to the nature
of the metal involved[ Representative examples have been chosen to demonstrate the synthetic
strategies[ Metal carbenes which are incapable of isolation\ but can be generated mainly by metal!
catalysed decomposition of diazo compounds\ are not included in this chapter ð83CR0980Ł[
Scheme 3
Scheme 4
vacuum
Cp2Ti + phosphine Cp2Ti (2)
49–77% Phosphine
(3) (4)
phosphine = PMe3, PMe2Ph, PEt3
PMe3
R R Cp2Ti
0–20 °C
Cp2Ti(PMe3)2 + (3)
R
R
(5) (6) (7) a; R = Me, 81%
b; R = Ph, 72%
PMe3 PMe3
PMe3 Cp2Zr Cp2Zr
Ph Ph 20 °C
Cp2Zr + + (6)
Ph Ph
Ph Ph
(12) (6b) (13) (14)
Me Me Me Me
Me Si Si Me i, MgBn2•2THF Me Si Si Me
Cl (7)
Zr ii, hν or ∆ (–Bn) P Zr P
P P
Pri Cl3 Pri Pri Pri
Pri Pri Pri
Pri Ph
(15) (16)
Me But
+ (Me2PCH2)2
+ Me P V
CpVCl2(PMe3)2 2ButCH2MgCl CpV(CH2But)2PMe3 Me
–C(Me3)4, –PMe3 P
Me
(17) (18) (19) (20)
Scheme 5
But But
2 LiCH2But, –78 °C 2L But
Cl2Nb(CH2But)3 (ButCH2)3Nb
83% 75% Nb
L L But
(21) (22) L = PMe3, PMe2Ph (23)
Scheme 6
toluene, 6 h But
Nb(CH2But)2Cl3 + TiCp Cp2ClNb (8)
(24) 42% (25)
But
–30 °C to 25 °C
Nb(CH2But)2Cl3 + THF Cl3(THF)2Nb (9)
(26) (27)
2LiCH2But But
Cl2Ta(CH2But)3 MeCMe3 + (ButCH2)3Ta (10)
TiCp
But
Ta(CH2But)2+nCl3–n Cp(ButCH2)nCl2–nTa (11)
(28)
n = 2 or n = 0
2L But
Ta(CH2But)2X3 X3L2Ta (12)
X = Cl, Br; L = PMe3, PPhMe2, PPh2Me, THF
2PMe3 Ph
TaBn2X3 (13)
70–79%
X3(PMe3)2Ta
X = Cl, Br
12 h Ph
TaBn3Cl2 + LiCp* (14)
70%
Cp*(Bn)(Cl)Ta
(29)
401 Doubly Bonded Metal Functions
2MeLi, Et2O CH2PMe3
Cp*2TaCl2 Cp*2(H)Ta Cp*2MeTa
80% ~100%
Scheme 7
Scheme 8
Formation of a carbene hydride complex from a tantalum alkyl complex is also possible[ The
carbene hydride complex "21# can be obtained in moderate yield as beige crystals by reducing
Ta"CH1But#Cl3 "20# with two equivalents of sodium amalgam "Equation "05## ð79JA5597Ł[ An
alternative route to the tantalum carbene complex "21# is via transformation of a carbene moiety
from a main group ylide to tantalum"III# under the appropriate conditions[ Two examples are shown
in Equation "06#\ and both the tantalum carbene complexes are thermally stable ð68JOM"060#32Ł[ On
photolysis in hydrocarbon solution with an ultraviolet light source\ the methyl complexes "22#
containing very bulky aryloxide ligands lose one equivalent of methane to form tantalum carbene
complexes "23# in essentially quantitative yields "Equation "07## ð75JA0491Ł[
Et2O/THF But
Ta(CH2But)Cl4 + 2Na/Hg + 5PMe3 (H)(PMe3)3Cl2Ta (16)
(31) (32)
OAr OAr
Me Ta Me hν
Me Ta (18)
Me ~100%
OAr OAr
(33) (34)
ArO = 2,6-di-t-butylphenoxide
2,6-di-t-butyl-4-methoxyphenoxide
A number of new tantalum carbene complexes can be prepared from preexisting tantalum carbene
complexes via modi_cation of the carbene ligand or the tantalum ligand[ The tantalum carbene
complex "24# reacts with two equivalents of LiOCMe2 to give "25# as light yellow crystals in 54)
yield "Equation "08## ð70JA0339Ł[ Similarly\ bulky tantalum carbene complexes containing phenoxide
or benzenethiolate ligands of type "27# can be prepared from the readily accessible tantalum carbene
"26# ð79JA5125Ł in good yield by analogous methods ð75OM1051\ 77JA3853\ 89IC0093Ł[ The related
pyridine and diethyl sul_de adducts "28# can be easily obtained from "27# in high yields "Equation
"19##[ Another interesting tantalum carbene complex "39# with the terdentate monoanionic 1\5!
bis"dimethylamino#methyl#phenyl ligand has been prepared in 89) yield starting from "26# "Equa!
tion "10##\ and it is thermally stable at room temperature ð89RTC335Ł[
(35) (36)
C1Mo Function 402
2,6-diisopropylphenoxide;
pyridine;
X= 2,6-dimethylphenoxide; Y=
SEt2
2,4,6-triisopropylbenzenethiolate
But
Me2N Li NMe2 Cl Cl
Ta
But –78 °C, Et2O Me2N NMe2
Cl3(THF)2Ta
+ (21)
90%
(37)
(40)
Ph Ph
Cl –20 °C
+ (CO)5CrNa2 (CO)5Cr (22)
Cl –NaCl
Ph Ph
(41) (42) (43)
Scheme 9
Scheme 10
i, DME
ii, 2.6-lutidine NAr i, R1CH2MgCl
Cl NAr
iii, TMS-Cl Me ii, 3TfOH
MoO2Cl2(THF) + 2ArNH(TMS) O Mo
95% Cl R1 = But, 65%
O
Me R1 = PhMe2C, 76%
(48)
NAr
TfO NAr
Me 2LiOR2
O Mo R1 R2O Mo
OTf 50–95%
O 1
Me OR2 R
(49) (50)
Ar = 2,6-diisopropylphenyl
R 2 = But, 2,6-diisopropylphenyl, 2-t-butylphenyl
Scheme 11
NAr
NAr ButO Mo
45–55 °C
ButO Mo + (23)
CO2Me ButO
But 90–95%
ButO MeO2C But
CO2Me
CO2Me
(50) Ar = 2,6-diisopropylphenyl (51)
Four!coordinate molybdenum carbene complexes that contain the t!butylimido ligand have been
prepared by the routes shown in Schemes 01 and 02[ Reaction of the molybdenum complex "41#
with ButNCO\ followed by alkylation with "ButCH1#1Mg resulted in the formation of the imido!
alkyl compound "42#[ Treatment of "42# with ButCH1Li then yielded the molybdenum carbene
complex "43# in 64) yield[ The new carbene complex "44# can be obtained by reaction of "43# with
Ph2SiOH "Scheme 01# ð76CC018Ł[ The molybdenum carbene complex "48#\ which is analogous to
"49#\ has been prepared by treatment of "45# with hexa~uoroisopropanol "Scheme 02#[ When "48# was
treated with a terminal alkene such as styrene\ its carbene ligand was exchanged stoichiometrically to
form the phenyl carbene complex "59#[ Five!coordinate molybdenum carbene complexes such as
"47# can be prepared from the key complex "46# by replacement of the t!butylamine ligand with
stronger Lewis bases "Scheme 02# ð78CC0951Ł[
NBut NBut
ButCH2 ButCH2
Ph3SiOH
Mo Mo
Ph3SiO
ButCH 2
But But
(54) (55)
Scheme 12
i, ButNCO NBut
ii, 2LiCH2But 2HOCH(CF3)2 (CF3)2HCO
MoO2Cl2 Mo(NBut)2(CH2But)2 Mo
81% 80% (CF3)2HCO But
(56) ButNH2
(57)
MeCN, vacuum L
Scheme 13
reported a general protocol for the synthesis of tungsten carbene complexes of the type "56#\ which
simply involves reaction of the oxo ligand!containing tungsten complexes "55# with aluminum
halides "Equation "14## ð71CC403\ 74CC682Ł[ In addition\ other types of tungsten carbene complexes
are readily prepared from "56# by a metathesis reaction ð76JA2842Ł[ The phenylimino tungsten
carbene complex "58# can also be synthesised from the readily available precursor "57# by using a
similar technique\ as shown in Scheme 04 ð89OM1151Ł[ In 0882\ oxygen! and moisture!stable tungsten
carbene complexes "69# containing a bulky hydridotris"pyrazolyl#borate ligand were prepared in
modest yields by an a!hydrogen abstraction reaction "Scheme 05# ð82OM1703Ł[
But But
100 °C, –CMe4
+ 2PMe3 ButCH2 (24)
ButCH2 W CH2But W
~100%
Me3P t
CH2But PMe3 Bu
(61) (62)
But But
But Cl Me3P•HCl Cl
Me3P
W W
60% Cl
NPh NPh
Me3P Me3P
(65)
Scheme 14
405 Doubly Bonded Metal Functions
O CH But But
2 + AlX3 X
ButCH2O W
ButCH2O W (25)
t
ButCH2O CH2Bu –CMe4
X
ButCH2O
(66) (67)
X = Cl, Br, I
i, ArNCO Me Cl NAr
ButO OBut
ii, 2 LiOBut PCl5, DME O W
ButCH2 W
WOCl4 O Cl
iii, 2 (ButCH2)MgCl
ButCH2 NAr 90% But
62% Me
(68) (69)
Ar = N-2,6-C6H3-Pri2
Scheme 15
NAr KHB N N N
NAr N NAr
Cl Cl 3ClMgR
RCH2 CH2R 3
W W HB N N W CHR
Cl Cl Cl CH2R
22–38%
OEt2 N N CH 2R
(70)
R = Me, Ar = Ph; R = Ar = Ph; R = Me, Ar = 2,6-Pri2C6H3
Scheme 16
Tungsten carbene complexes can be prepared from the corresponding complexes containing the
carbonÐtungsten triple bond[ Thus\ reaction of the carbyne complexes "60# with two equivalents of
HX "XCl\ Br\ MeCO1\ OPh\ OC5F4\ O!p!C5H3Cl# gave the carbene complexes "61# "Equation
"15## ð74OM0826Ł[ The halide complexes are the least thermally stable members of this class\ while
the carboxylate derivatives appear to be quite stable[ Protonation of the carbonyl!containing carbyne
complexes "62# in dichloromethane with excess concentrated HCl at room temperature gave the
tungsten carbene complexes "63# "Equation "16## ð76OM322Ł[ Lewis acid!free\ four!coordinate tung!
sten carbene complexes "67# have been prepared from the tungsten carbyne complex "64#\ as shown
in Scheme 06 ð75JA1660Ł[ Catalytic proton transfer in the carbyne complex "65# to give the tungsten
carbene complex "66# is the key step in the synthesis[ All these reactions proceed in high yield[ The
asymmetric tungsten carbene complexes "70# and "71# have been prepared via reactions analogous
to those shown in Equation "15#[ The carbyne complex "68# reacts with one or two equivalents of
the ligand "79# to give "70# and "71#\ respectively "Scheme 07# ð82OM1454Ł[
ButO X
+ 2HX ButO
ButO W But W (26)
–ButOH ButO
ButO X But
(71) (72)
X = Cl, Br, MeCO2, OPh, OC6F5, O-p-C6H4Cl
Scheme 17
ButO
ButO W Ph
ButO
(79)
OH OH
2
OH OH
–ButOH –3ButOH
(80) (80)
Ph Ph
O W OBut O W O
O OBut O O
(81) (82)
Scheme 18
pentane
Ta(CHBut)X3L2 + W(O)(OBut)4 Ta(OBut)X + W(O)(CHBut)X2L2 (28)
(85) (86) (87)
L = PMe3 or PEt3; X = Cl or Br
407 Doubly Bonded Metal Functions
O PMePh2
–2PMePh2 Cl W
WCl2(PMePh2)4 + 2 O (29)
–cyclopentanone Ph2MeP
(88) Cl
(89)
NPh NPh
Cl PMePh2 Ph3P –PPh3 Cl PMePh2
W + W (30)
Ph2MeP PMePh2 R –PMePh2 Ph2MeP CHR
Cl Cl
(90) (91) (92)
NAr NAr
80 °C, 2 h Cl P(OMe)3 2LiOR RO P(OMe)3
NAr W W
Cl P(OMe)3 Ph –P(OMe)3 (MeO)3P –78 °C (MeO)3P
W + Cl RO
(MeO)3P P(OMe)3 Ph 72% Ph 64% Ph
Cl
Ph Ph
(93) (94) (95)
Ar = 2,6-C6H3Pri2; OR = OCMe(CF3)2 or O-2,6-C6H3Pri2
Scheme 20
Finally\ a variety of new tungsten carbene complexes can be prepared from preexisting tungsten
carbene complexes[ Thus\ the carbene complexes "85# were readily obtained from "56# by metathesis
reactions involving a terminal alkene\ as shown in Scheme 10 ð76JA2842Ł[ Further reaction of "85#
with one equivalent of Li"OCH1But# then yielded trineopentoxo complexes "86#[ In addition\ the
_ve!coordinate tungsten carbene complex "88# can be prepared from the corresponding six!coor!
dinate carbene complex "87# by scavenging one phosphine ligand with PdCl1"PhCN#1 "Equation
"20## ð71OM037Ł[
Br Br ButCH2O
+ H2C=CR1R2
R1 Li(OCH2But) (1 equiv.) R1
ButCH2O ButCH2O ButCH2O
W W W
ButCH2O – H2C=CHBut ButCH2O pentane ButCH2O
Br But Br R2 Br R2
69–98%
(67) (96) (97)
Scheme 21
Pd(PhCN)2Cl2
W(O)(CHBut)Cl2(PEt3)2 W(O)(CHBut)Cl2(PEt3) (31)
80%
(98) (99)
MeLi, –50 °C
[Cp(CO)2Mn≡CMe]+BCl4– Cp(CO)2Mn (32)
15%
(100) (101)
O
–N2, –THF
Ph Mn Ph
Mn + Ph OC (33)
OC THF 37% CO
CO N2
O Ph
R1 –N2, –THF
R1
MnCp(CO)2(THF) + N2 Cp(CO)2Mn (34)
R2 72–82% R2
=
R2 R1 Ph Ph
+ +
R1 [R2]–
R1 H+ or CF3SO2-TMS R1
Cp(CO)LFe Cp(CO)LFe R2 Cp(CO)LFe
OMe OMe R2
(102) (103) (104)
L = CO, PMe3, PPh3; R1 = Me, Et, Pri, Bun, Ph, C6H4-p-Me, c-C3H5; R2 = H, Me
Scheme 22
419 Doubly Bonded Metal Functions
+
R1 FSO3Me R1 R1
25–100 °C
Cp(CO)2Fe R2 Cp(CO)2Fe R2 Cp(CO)2Fe
or Me3O+BF4– + SMeR3
SR3 R2
(105) (106) (104)
R1 = H, Me, Et; R2 = H, Me; R3 = Me, Ph
Scheme 23
An alternative approach to the preparation of iron carbene complexes "009# is through pro!
tonation of h0!vinyl iron complexes "098#[ The h0!vinyl iron complexes "098# can be prepared from
either the sodium ferrate "096# or the iron iodide "097#\ as shown in Scheme 13 ð71JA2650\ 71JA5008Ł[
R2
O R2
R1
Cp(CO)2Fe–Na+ +
Cp(CO)2Fe
Cl R1
(107) O
–CO
hν 60–90%
+
R2 R2 HBF4
R2
Cp(CO)2FeI + M Cp(CO)2Fe Cp(CO)2Fe
25–40%
R1 R1 R1
(108) M = Li or MgBr (109) (110)
Scheme 24
CH2N2
RuCl(NO)(PPh3)2 Cl(NO)(PPh3)Ru (35)
(111) (112)
Ph Ph
CH2Cl2/PhH, 53 °C, 11 h
RuCl2(PPh3)n + (36)
Ph ~100% Cl2(PPh3)2Ru Ph
(113)
n = 3 or 4
Ph
Pri3Sb N2 Pri3Sb Ph Ph
Ph NaCp
Cl Rh Cl Rh Rh
96% 78%
Pri3Sb Pri3Sb Ph Pri3Sb Ph
(114) (115) (116)
PPri3 L
4SbPri3 87–89%
98%
82%
[RhCl(C2H4)2]2 Pri3P Ph
Ph
Cl Rh Rh
Pri3P Ph L Ph
(117) (118)
L = CO or CNBut
Scheme 25
But
4HCl 3ButCH2MgCl
Re(NBut)3(O-TMS) Re(NBut)2Cl3 ButN Re
–TMS-OH –CMe4 But
ButN
(119) (120)
Scheme 26
THF, RT Cp(CO)2Re
Cp2Zr(η2-COR)Cl + K+Cp(CO)2ReH– (37)
52–58% R
(121) (122) (123)
R = Me, CH2CH2But
Scheme 27
Oxocarbene complexes "017# have been prepared in 65) isolated yield by photolysis of
the rhenium cis!dioxo complex "016# in pyridine\ as shown in Equation "27# ð77CC0378Ł[
411 Doubly Bonded Metal Functions
Nonheteroatom!stabilised rhenium carbene complexes have been synthesised from the reaction of
cationic rheniumÐcarbyne complexes[ Thus\ addition of diethylaluminum hydride or methyllithium
to the phenylcarbyne complex "029# has a}orded the rhenium carbene complexes "018# and "020#\
in 63) and 35) yields\ respectively "Scheme 17# ð65JOM"019#C5\ 67CB2639Ł[ Furthermore\ a series of
new rhenium carbene complexes can be prepared from preexisting rhenium carbene complexes[
Addition of excess gaseous hydrogen chloride to rhenium carbene complexes "021# in di!
methoxyethane yielded the rhenium complexes "022# in 74) yield[ Addition of excess t!butylamine
to "022# then a}orded the new carbene complex "023# in 84) yield\ as bright yellow _bres "Scheme
18# ð81JA2256Ł[ Similarly\ four!coordinate rhenium carbene complexes "026# can be prepared in a
manner analogous to that described for "023#[ Thus\ addition of two equivalents of gaseous hydrogen
chloride to the carbene complex "024# a}orded the rhenium complex "025# in high yield[ The complex
"025# reacts with two equivalents of lithium or potassium alkoxide to give "026# quantitatively
"Scheme 29# ð81JA2256Ł[
hν, pyridine
But
ReO2(CH2But)3 O Re (38)
76%
O But
(127) (128)
Et2AlH LiMe
Cp(CO)2Re –78 °C, 15 min –40 °C, 8 h
[Cp(CO)2Re≡CPh][BCl4] Cp(CO)2Re
Ph 74% 46% Ph
(129) (130) (131)
Scheme 28
t
ButH2N Bu
6HCl, DME ButNH 2 (excess) Cl
2Re(NAr)2(CHBut)(CH2But) [Re(CBut)(CHBut)(ArNH2)Cl2]2 2 Re
–ArNH3Cl 95% Cl
But
ButH2N
(132) (133) (134)
Ar = 2,6-C6H3Pri2, But
Scheme 29
+2HCl But
–2H2O +2MOR
Re(O)2(CHBut)(CH2But) 1/ [Re(CBut)(CHBut)Cl ]
x 2 x
RO
~100%
Re
85% RO
But
(135) (136) (137)
M = K, Li; R = But, CMe2(CF3), CMe(CF3)2, 2,6-C6H3Pri2, SiBut3
Scheme 30
Ph Ph
CH2Cl2/PhH
OsCl2(PPh3)4 + (40)
Ph ∆ Cl2(PPh3)2Os Ph
(143) (144)
Copyright # 1995, Elsevier Ltd. All R ights Reserved Comprehensive Organic Functional Group Transformations
3-16
Ketenes, their Cumulene
Analogues and their S, Se
and Te Analogues
DAVID C. HARROWVEN and SHELAGH T. DENNISON
University of Southampton, UK
3.16.1 KETENES 525
3.16.1.1 From Acid Halides 526
3.16.1.2 From 2-Haloacyl Halides 530
3.16.1.3 From a-Diazocarbonyl Compounds 530
3.16.1.4 From Carboxylic Acid Anhydrides 534
3.16.1.5 From Other Acyclic Ketones, Carboxylic Acids and their Derivatives 535
3.16.1.6 From Carbocyclic Ketones and Related Compounds 537
3.16.1.7 From Alkoxyalkynes 540
3.16.1.8 From Heterocyclic Materials 541
3.16.1.9 From Transition Metal Complexes 544
3.16.1.10 Miscellaneous Methods 545
3.16.2 THIOKETENES 546
3.16.2.1 From Ketenes and Thioketenes 546
3.16.2.2 From Acid Chlorides and Thioacyl Chlorides 547
3.16.2.3 From the Sulfur Analogues of Carboxylic Acids and Esters 547
3.16.2.4 Via Alkynyl Sulfides and Alkynyl Thiolates 548
3.16.2.5 From Sulfides of Carbon 549
3.16.2.6 From Ketene-S,X-Acetals 550
3.16.2.7 From Heterocyclic Materials 550
3.16.2.8 From Vinylidene Transition Metal Complexes 552
3.16.3 SELENOKETENES 553
3.16.1 KETENES
Ketenes are inherently reactive species that show a strong tendency to dimerise, suffer nucleophilic
attack or undergo aerial oxidation. As a result, they are often difficult to isolate and relatively few
have been properly characterised. The stability of a ketene is, however, greatly influenced by
its substituents. Dialkylketenes are considerably more stable than the corresponding monoalkyl
derivatives; for example, dimethylketene dimerises at room temperature in about an hour whilst
methylketene suffers this fate in just a few minutes. Electronic factors also play an important role,
with phenyl, silicon, germanium and tin substituents imparting a stabilising effect on the system.
Halogen and chalcogen substituents, by contrast, tend to accelerate the polymerisation process.
For synthetic purposes the instability of a ketene is often of little consequence, especially when
an in situ preparation is available. In this chapter, therefore, those processes that have resulted
unambiguously in the formation of ketenes are presented alongside those for which it is reasonable
525
526 Ketenes, Cumulenes and S, Se and Te Analogues
to assume their intermediacy. Limitations on space prohibit a truly comprehensive overview. The
interested reader is therefore directed to the excellent monologues by Ward <B-8OMI 316-01 >, Buehler
and Pearson <B-70MI 316-01), Luknitskii and Vovsi <69RCR487>, Borrmann <68HOU(7/4)65>, Lacey
<B-64MI 316-01 >, Wagner and Zook <B-53MI 316-01 >, Hanford and Sauer <46OR(3)l08>, and the remark-
able pioneer of ketene research Staudinger <B-12MI 316-01 >, for additional examples of ketene
syntheses.
(i)
The mechanism through which this conversion occurs has been subject to much speculation. It is
now generally accepted that ketene formation arises through the collapse of an intermediate acyl
ammonium salt (49JA2242, 52JA4962, 62CJC2362). Some confusion arose when a series of experiments
revealed that the dehydrohalogenation of a-haloacyl halides by tertiary amines first led to the
formation of enolate salts <68HCA1466, 68TL1977, 70HCA120, 70JOC1515>. These studies appeared to
suggest that a second mechanistic route to ketenes might be operative <73JA7447>. This idea was
dispelled by Brady and Scherubel when they showed that the two salts could be interconverted, by
the series of equilibrations outlined in Scheme 1, and that the reactions each exhibited were distinct
<74JOC3790>. The observation that sodamide may be used in the analogous preparation of di-r-
butylketene from the corresponding acid chloride would appear to be exceptional (60JA2498,81T4189).
Scheme 1
Nevertheless, the propensity for the deprotonation of acid halides by amine bases introduces
some additional complications to this protocol as exemplified by the formation of the vinyl ester (2)
when the dichloride (1) was treated with triethylamine (Equation (2)) <68TL6003>. This difficulty can
be circumvented by the slow addition of the acyl halide to a solution of the amine <74JOC3790>.
(2)
The fact that this protocol has found most favour for the in situ generation of ketenes may also
be due to the presence of residual trialkylammonium hydrohalides. These have been shown to
catalyse the addition of nucleophiles to ketenes and many of the cycloaddition reactions they
undergo. Unfortunately, the rate of polymerisation of ketenes is also dramatically increased and so
their isolation is rendered more difficult.
As a preparative route for the in situ generation of ketenes, this is of little consequence and
Ketenes 527
countless references to its use could be cited. There would appear to be few limitations and the list
of ketenes that have been accessed in this fashion is impressive. These include simple di- and
monoalkylated ketenes, aryl-, vinyl-, acyl- and allylketene together with an array of ketenes bearing
heteroatom substituents. The examples in Table 1 serve to illustrate the diversity in application of
this synthetic entry.
o * °
67T4769 68CB1120 70TL3657 77JOC2111 57JA6261
76JOC3303
Interestingly, when a,j9-unsaturated acid halides are exposed to tertiary amines, the products
usually appear to implicate the intermediacy of the corresponding methyleneketenes <66JOC718>. In
all the examples investigated to date, this assumption has been shown to be erroneous <B-80MI 316-03)
and the reaction actually proceeds via 1,4-dehydrohalogenation. Trapping of the resulting vinyl-
ketene then leads to a /?,y-unsaturated ketone, which suffers alkene migration under the conditions
employed, as, for example, in Scheme 2 <7OHCA2159>.
Scheme 2
The use of pyrolysis or photolysis to initiate elimination of HCl from acid chlorides has, by
comparison, received scant attention. The thermal decomposition of acetyl chloride to ketene has
been established for many years <77AG(E)1O5>, but extensions are few and have tended to be confined
to 0^/z0-substituted aroyl halides. The pyrolysis of salicyloyl chloride, for example, provides ready
access to the highly reactive ketoketene (3; X = O) <68M1958>, whereas ortho-toloy\ chloride and
528 Ketenes, Cumulenes and S, Se and Te Analogues
related homologues yield products derived from the corresponding vinylketenes (Scheme 3)
<77AG(E)469>.
Scheme 3
In the 1980s and 1990s, considerable attention has focused on the synthesis of ketenes that bare
chiral substituents as they offer a convenient and enantioselective entry towards /Mactams by
means of a ketene-imine cycloaddition <81CC344>. Several encouraging developments of this general
stratagem have been reported, of which two examples are highlighted (Schemes 4 and 5) <91TL1O39,
92TL4823).
Scheme 4
Scheme 5
Synthetic entries towards several other naturally occurring ring systems have incorporated this
methodology as a key feature. Oppolzer and Nakao, for example, explored an ingenious entry
towards 6-protoilludene (6) in which the conversion of the acid chloride (4) to the ketene (5) with
Pr' 2 EtN played a pivotal role (Scheme 6) <86TL547l>. A strategically similar approach to isocomene
(11) by Snider and Beal proved equally rewarding. Thus, when the mixture of acid chlorides (7)
was treated with triethylamine, the tricyclo[5.3.0.0]decane (9) was provided via an intramolecular
[2 + 2] cycloaddition of the transient ketene (8). Isomerisation of the exo-cyclic alkene in (9) to (10)
using HI then completed a formal total synthesis (Scheme 7) <88JOC4508>.
Scheme 6
Syntheses of a diverse array of terpenes have utilised this strategy <82JA747, 87CC1728, 88CC1421,
91JOC321). Few have been as efficient as that described by Corey et al. in their total synthesis of
retigeranic acid (12) (Scheme 8) <85JA4339>. An interesting extension was described by Brady et al.
who found that treatment of the acid chloride (13) with triethylamine initiated sequential ketene
Ketenes 529
Scheme 7
formation, cycloaddition and decarboxylation giving the benzofuran (14) in high yield (Scheme 9)
<86JOC2145>. The in situ generation and intermolecular trapping of ketenes by alkenes has found more
general application. For example, in the early stages of Ghosez's approach to the prostaglandins,
dehydrohalogenation of the acid chloride (15) first produced the ketene (16) which was then trapped
with cyclopentadiene to give the bicycle (17). A short sequence of standard transformations was then
established to convert this material (17) into the Corey intermediate (18) (Scheme 10) <8UA4616>.
Scheme 8
Scheme 9
Scheme 10
530 Ketenes, Cumulenes and S, Se and Te Analogues
3.16.1.2 From 2-Haloacyl Halides
The preparation of ketenes by dehalogenation of 2-haloacyl halides was first described by Stau-
dinger in 1905 and remains to this day a popular and convenient route to these materials (Equation
(3)) <05CB1735>. The most common method used to accomplish this conversion involves the treat-
ment of an ethereal solution of the dihalide with zinc <82JOC387l, 93S606). In later years this has
often been used in the form of a zinc-copper couple <9UOC7048> where the presence of phosphoryl
chloride may be beneficial (78JOC2879, 87JOC4885). Other reagents such as magnesium <O9CB4213>,
silver <08LA(356)51>, mercury <46OR132>, triphenylphosphine <68JOC3974> and pentacarbonyl-
manganate salts <86JOC3558> have also been successfully employed, and would appear to be advan-
tageous in some cases.
(3)
Various methods have been described for the isolation of ketenes prepared in this manner. When
sufficiently inert, residual salts may be removed by aqueous workup, though this is more commonly
achieved by distillation under reduced pressure <63OSC(4)348, 86S43>. In the cases of methyl- and
dimethylketene, higher yields have been observed when the reaction is conducted under reduced
pressure with the ketene removed, in solvent, as it is formed <63OSC(4)348,75JCS(P1)16OO>.
The reaction has also been widely used as a convenient method for the in situ generation of ketenes
<62AG32>. Their intermediacy is usually inferred but may often be established more rigorously by
spectroscopic means (e.g., by a strong infrared active band at ca. 2130 cm" 1 ) <B-80MI 316-02). This
has greatly increased the scope of this methodology, and numerous examples have now been
documented (Table 2).
The fact that this method has not found as much favour as the dehydrohalogenation of acid
halides may reflect the greater synthetic challenge involved in the preparation of the requisite starting
materials, though the presence of residual zinc bromide may also be deleterious.
The precise manner in which the ketene is formed has been the subject of considerable debate,
and there would appear to be no single mechanistic description for the reaction. In fact, there is
compelling evidence for both concerted <85JA7597> and nonconcerted rearrangement, the latter
involving the intermediacy of a-ketocarbenes <88JA1O25> and oxirenes (Scheme 11) <72JCS(P2)2623,
80PAC1623, 83CRV519, 85JOC135>. An overview containing numerous pertinent references has been
presented by Gill, and the interested reader is referred to this text for further details <91COS(3)887>.
While the production of a ketene intermediate is a pivotal feature of the Wolff rearrangement,
these species are seldom isolated. The reaction is most widely used for the preparation of carboxylic
Ketenes 531
Table 2 Various routes to ketenes involving dehalogenation of a-halo acylhalides.
z
Br X « \^**0 II Zn
*°
Br
>^*< —- Y -^Br ^
63OSC(4)348 PPh3,68JOC3974
ZnorMg,09CB4213
0 O °
87JOC4885 05CB1735
78JOC2879 93CB297
,— ph ci /—\ Ph fl ^ n ^%
II Mn(CO)5- ^O ||
86JOC3558 Ph
88JOC4877
Scheme 11
acids, esters and amides and is therefore well represented in other chapters. The limited discussion
presented here reflects this fact.
Several methods to initiate the Wolff rearrangement have been described. Typically, the decompo-
sition of a-diazoketones is achieved by exposure to light <59CB528>, heat <82CPB526> or transition
metals <4UOC669>. Each of these methods has limitations. Thermolysis of these materials often
requires temperatures in the region of 200 °C, where other electrocyclic processes may also be facile
<91COS(3)887>. The addition of transition metal catalysts lowers the decomposition temperature
appreciably but these may alter the reactivity profile of the carbene intermediate. Rhodium, pal-
ladium and copper catalysts, for example, readily form complexes with these carbenes and are
normally avoided when ketene formation is desirable <B-71MI 316-01, B-78MI 316-0l>. Most commonly,
WolfFs original catalyst, freshly prepared silver oxide, is employed together with either sodium
carbonate or a tertiary amine <35CB85O, 71T1317). Silver salts such as the benzoate <70OS(50)77> or
532 Ketenes, Cumulenes and S, Se and Te Analogues
nitrate <58JOC1166> have also found common usage. A selection of illustrative examples are collected
in Table 3.
0 r -,
JL hv ^0 HSEt II
59CB528
|1
N2
' ^' ' \ASEt
o r 1 i 1 o
. 11 , A 1 -*° PhCH2OH 1 U
YY ^^^f~ " ^ Y ^ O Ph 82CPB526
' N2 SO2Bn S0 2 Bn
/ V n [ 0
41JOC669
i^Xx L
r y : J
fX ^
N2
O r -i
N
\ — \ /=' =O \ /~C02H
° [ *°1 if
rn
^ ^ ^ ^ Y ^ ^ T Ph y NH2 48JCS1674
N2 L / J ^/
O^^^. °*. CO2Et
r^Yi "^S0B^ I ^ V ^ J
^^ f \ * \ 70OS?7
The greatest drawback of this method is the number of competing side reactions that may occur.
Diazoketones are themselves very reactive species which can participate in 1,3-dipolar cycloadditions
<(38CB1179>, suffer attack by soft nucleophiles <63CB1948), undergo other rearrangements
<85JOC280l), and react in aldol-type condensations <72S35l>. The ketocarbene intermediate adds to
these difficulties; being prone to collapse by 1,2-hydrogen shift <72JCS(Pl)2623>, inter- and intra-
molecular hydrogen abstraction <B-71MI 316-01, B-78MI316-01), insertion into vicinal carbon to carbon
and other sigma bonds <70JA6706> or through cycloaddition to an appropriately situated Tt-system
<68BSF4913>. Perseverance often holds the key to success. For example, when the diazoketone (19)
was exposed to copper salts, the product of carbene insertion (21) predominates. By contrast,
photolytic rearrangement of (19) leads to the bicycle (23) via the intermediate ketene (22) (Scheme
12) <65CI(L)424, 65CI(L)425>.
Increasingly, the photolytically induced Wolff rearrangement has found favour <84SC163,
85JOC4404). On many occasions, a greater selectivity towards ketene formation is observed when
this method, rather than the thermolytic and transition metal-catalysed variants, are employed
<51LA(573)17,52CB225,55CB934). This has been attributed to a lesser tendency to exhibit carbenoid
insertion reactions. Most commonly, irradiation is conducted at 0°C using a medium pressure
mercury arc. The use of higher energy photons and elevated temperatures has, on occasions, been
profitable though complications associated with the photolabile nature of the products may arise
(66T209, 69T2121).
While carbene insertion usually prevents ketene formation, in the vinylogous Wolff rearrangement
it is a prerequisite for their formation <74JOC3355>. Thus, when /?,y-unsaturated diazoketones are
exposed to copper(II) salts, the intermediate carbene is intercepted by the vicinal alkene with the
generation of a bicyclo[2.1.0]pentanone. Rupture of this highly strained intermediate then provides
the ketene which is usually trapped in situ by a suitable nucleophile (Scheme 13).
Ketenes 533
Scheme 12
Scheme 13
The yields and degree of selectivity observed in this process are moderate to high, and it has
found many applications <84JA3995, 84JA4001, 86TL3913). A few illustrative examples are given in
Schemes 14^16. Interestingly, /?,>>-unsaturated diazoketones can also be encouraged to undergo
normal Wolff rearrangement through exposure to silver ions or by conducting the reaction under
thermolytic or photolytic conditions. These processes are however, prone to give complex mixtures
arising from the competitive vinylogous rearrangement <74CC695, 76JA7456, 77JOC3165,84JOC2052).
Finally, it has been shown that a-silyl- and a-germyl-a-diazocarbonyls may be converted into
bismetalloketenes by treatment with bis(triethylsilyl)mercury (75IZV199, 76ZOB930).
Scheme 14
Scheme 15
Scheme 16
534 Ketenes, Cumulenes and S, Se and Te Analogues
3.16.1.4 From Carboxylic Acid Anhydrides
In 1907 Wilsmore and Stewart disclosed their finding that the immersion of a hot platinum wire
into acetic anhydride could be used to generate ketene, H ; C==G=O <O7JCS1938). While this process
was of little preparative use, subsequent modifications to the procedure have established this source
of the parent compound invaluable for the preparation of ketene in the laboratory <53JOCI055>.
The method has also found application in the synthesis of other ketenes in moderate to high yield
<61CP6!8722.68MI 316-03). For example, pyrolysis of isobutyric anhydride to dimethyl ketene (68M1316-
01), and the preparation of silyl- and germylketenes from the requisite met a Elated acetic anhydrides
produced these materials in good yield and a high state of purity (Equation (5)) <69ZOB467,70ZOB707).
(5)
Another convenient route to ketenes involves the pyrolysis of malonic acid anhydrides <08CB2208.
13CB3539). These materials, on gentle warming (100"C) under reduced pressure, readily extrude
carbon dioxide with the liberation of a ketene (Equation (6)). The synthetic value of this entry lies
in the preparation of dialkylketenes where yields in excess of 50% are usually achievable <23HCA29i,
63AG(E)608>. The reaction is capricious, especially when the anhydride is prepared HI situ by dehy-
dration of the malonic acid derivative with acetic anhydride. Extreme care has to be exercised to
remove all traces of residua! acetic anhydride from the vessel prior to thermolysis if side reactions
are to be avoided. An alternative, more forgiving protocol has been developed in which isobutyric
anhydride is used to accomplish dehydration of the malonic acids <63AG{E)608).
(6)
A variety of mixed anhydrides of malonic acids have also been employed in the synthesis of
ketenes. Commonly, these are either the diphenylacetic anhydride (Scheme 17), interestingly pre-
pared by the action of diphenylketene on the malonic acid derivative <I3CB3539>, or the bis(tri-
fluoroacetic) anhydride, formed by reaction with trifluoroacetic anhydride (TFAA) <62JOC3146>.
Again, decomposition of these materials is usually effected by the action of heat, but in the latter
instance may also be accomplished using triethylamine (Scheme 18) <90CPB]60!>.
Scheme 17
Scheme 18
Ketenes 535
The synthesis of vinylketenes can be achieved by flash vacuum pyrolysis of crotonic anhydrides.
This method has been exploited in a synthesis of sibirinone (23), a metabolite of Hypomyces
semitranslucens G. Arnold (Scheme 19) <82JA6779>.
Scheme 19
3.16.1.5 From Other Acyclic Ketones, Carboxylic Acids and their Derivatives
The preparation of ketene by pyrolysis of either acetone or ethyl acetate was among the first routes
towards this compound (07JCS1938,07NAT510,07PCS229). In the following years it was established that
almost any molecule containing a methyl group directly bound to a carbonyl will liberate ketene on
thermolysis. Thus, syntheses of ketene through the action of heat on acetic acid <29JA3614>, biacetyl
<25JA1779>, acetaldehyde <25BRP273622>, together with numerous methylalkyl ketones <23JA3095>,
acetic esters <23JA2167> and amides <32JA2432> have been established (Scheme 20).
Scheme 20
The preferred method to accomplish these conversions consists of passing a vaporised sample
over a heated metallic surface. A detailed overview of the experimental procedures that have been
established was presented by Hanford and Sauer <46OR132>, and the interested reader is directed to
this account for further information. For most laboratory-scale uses, the generation of ketene by
pyrolysis of acetone has found most favour <40JOC122,46OR132).
One drawback of the protocol is that it fails to provide a general synthetic entry towards
homologous ketenes owing to the difficulties associated with the control of cracking processes. The
elevated temperatures necessary to induce fragmentation of ketones, for example (typically > 600 °C)
also induce rupture in pendant side chains; as exemplified by the thermolytic conversion of diethyl-
ketone to ketene rather than the anticipated methylketene <23JA3095>. In spite of these difficulties,
these reactions are not without synthetic value. For example, Streith and Tschamber found that,
although pyrolysis of butanone provided a 7:3 mixture of ketene and methylketene, the rate of
reaction of the latter with imines was several powers often greater than that observed with ketene.
536 Ketenes, Cumulenes and S, Se and Te Analogues
Consequently, good yields of 8-methyl-5-azanonamdienes could be obtained by exposure of the
corresponding diazepines to the pyrolysis gas of butanone (Scheme 21) <83LA1393>.
Scheme 21
There are, however, a growing number of exceptions to this rule. The pyrolysis of higher homo-
logues of aliphatic carboxylic acids have been used successfully in the generation of a variety of
mono- and dialkylketenes <63CI(M)1216>, and high yields of these materials have been reported
when the reaction is conducted in the presence of catalytic quantities of triethylthiophosphate
<60GEP1081455>. In exceptional cases, dehydration has even been achieved using phosphorus pent-
oxide <72ZOR654>. More recently, other dehydrating agents have been developed that achieve this
conversion under considerably milder conditions<87JOC3457,91S1027,92CB571 > as exemplified by Funk
et al. in their total synthesis of clovene (24) (Scheme 22) <88TL1493>.
Scheme 22
The thermally induced degradation of alkylphthalimides (Equation (7)) and also dehydration of
malonic acid monoesters, have found general application, since both of these processes may be
accomplished at greatly reduced temperatures <35JA774>. In addition, there exist a plethora of
synthetic entries to specific classes of ketenes. For example, phenylketene may be prepared by
irradiation of benzoyldimethylsulfonium methylide (64JA4866, 66JA1587) while the generation of the
acylketene (26) may be accomplished by dehydrohalogenation of 2-bromocyclohexane-l,3-dione
(25) (Scheme 23).
(7)
Scheme 23
provides a smooth entry towards ketenes (Equation (8)) <68MI 316-02), a process that has found
considerable use in the synthesis of vinyl acetates <60JA320l, 65JOC2502).
Scheme 24
Scheme 25
(8)
Finally, it should be mentioned that some useful entries to metalloketenes have been reported.
Rathke et al. have uncovered two unusual routes to bis(trimethylsilyl)ketene. First, they showed
that this material could be prepared from /-butyl bis(trimethylsilyl) acetate simply by generation of
its lithium enolate (Scheme 26) <77JOC2038>, and second through sequential treatment of tri-
methylsilylketene with butyllithium (— 100°C) and trimethylsilyl chloride (Scheme 27) <78JOC376>.
The former has now been extended towards a variety of dialkylketenes <85JA5396>.
Scheme 26
Scheme 27
Bryce-Smith and co-workers have also prepared copper(I), silver(I) and gold(I) ketenides
<70JCS(D)699, 73CC921, 74CC513). In a typical procedure, silver ketenide is formed by the action of
acetic anhydride on silver acetate in the presence of pyridine (Equation (9)) <7lGP2047373>.
(9)
been implicated in many other cases including the photochemical interconversion of the bicycles
(29), (30) and (31) (Scheme 29) (62JA4148, 62TL221, 62TL1297, 64CB1799, 68JA2449).
Scheme 28
Scheme 29
The diradical intermediate produced by a Norrish cleavage of this type may also yield ketenes by
other means. Thus, when 5,5-dimethylcyclopentenone was subjected to photolysis, the cyclo-
propylketene (32) was generated by recombination of the radical species through the allylic carbon
centre (Scheme 30) <69TL4517>. A similar rearrangement occurs when ethano-bridged anthracenes
are subject to irradiation, as exemplified by the conversion of (33) into ketene (34). These systems
are also prone to undergo cycloreversion, with the release of anthracene and the generation of
highly reactive cumulated ketene (Scheme 31) (68TL4995,73JA6294,77JA4554). Indeed, it is this process
that prevails when the related saturated analogues are photolysed <77T389>.
Scheme 30
Scheme 31
Scheme 32
In fact, ketenes may be accessed from almost all cyclobutanone derivatives. The photochemically
induced fragmentation of the parent system has been established for many years (67TL545, 72JA663,
Ketenes 539
Scheme 33
The thermally induced, electrocyclic ring opening of cyclobutenones (68JA2449,85JA3392) had, for
many years, received scant attention. However, the use of this protocol in a highly imaginative
synthesis of A-6-tetrahydrocannabinol by Kowalski and Lai (Scheme 34) <88JA3693> and related
entries towards benzoquinones <85JA3392, 86JOC3067> and bicyclo[3.2.0]heptenones <9UOC6094>
described by Moore et al. will undoubtedly inspire further exploration of this chemistry.
Scheme 34
Scheme 35
(10)
540 Ketenes, Cumulenes and S, Se and Te Analogues
Scheme 36
(11)
(12)
(13)
The resulting ketenes usually react with the parent alkyne to afford a cyclobutanone (Scheme 37)
<85S1118>, or they suffer attack by a suitable nucleophile (Scheme 38) <93TL207l>. However, when
silyl- <65DOK(164)357,68DOK(164)892> and germyl alkoxyalkynes are thermolysed, the increased stab-
ility of the resulting ketene allows these materials to be isolated by simple distillation <65DOK(179)357,
90JOC395). By contrast, when ethoxy(trimethylstannyl) acetylene was thermolysed, only bis(tri-
methylstannyl) ketene was obtained <73AG(E)675>. More conveniently, dimetalloketenes (Si, Ge, Sn,
B and combinations thereof) may be prepared from the requisite metallated alkoxyacetylene in
moderate to high yield by the action of R3MBr (M = Si, Ge or Sn) in the presence of magnesium
bromide <71ZOB240, 73AG(E)675> or exposure to boron trihalide (Scheme 39) <84ZOB1817>.
Scheme 37
Alkyl (trimethylsilyl)ketenes may also be accessed from alkyl alkoxyacetylenes by treatment with
trimethylsilyl iodide (Equation (14)) <79S740>. A substantial improvement to this procedure has
Ketenes 541
Scheme 38
Scheme 39
(14)
been developed by Kocienski and Pons during their syntheses of tetrahydrolipstatin <89TL1833> and
(-)-lipstatin (Scheme 40) <93JCS(P1)1549>.
Scheme 40
Scheme 41
Scheme 42
containing the a-diazo-y-lactone (36) is subject to photolysis (Scheme 44) <J5JA6586>. Interestingly,
this reaction proceeds via the ketene (37) and has been extended towards o-quinonoid methyl-
eneketenes, for example, (39) (Scheme 45) (75JA6586,80TL343).
Scheme 43
Scheme 44
A number of routes to o-quinonoid ketenes from condensed heteroaromatics have also been
disclosed, a selection of which are highlighted in Scheme 46 (62JOC3365,64M1053,66TL3465,68JCS(C)2730,
70JA7001, 7UCS(C)3328, 72CC451, 72TL3443, 73JA406l>. In each case acyl-, thioacyl- or iminoketenes are
Ketenes 543
Scheme 45
provided, and some parallels can be drawn between these entries and the more generally applicable
routes to such materials outlined in Scheme 47 <72TL1849, 73JA244, 73CC247, 73JA247, 73JA248,73JA5412,
73TL2875, 74HCA2583, 75AG(E)636, 75CPB2933, 76TL2961, 79TL59, 84H(22)2563, 85S224, 90CPB94, 90TL3677,
91T5689, 92S977).
Scheme 46
Scheme 47
Scheme 48
(15)
Scheme 49
Scheme 50
(16)
Several routes to c-bound metalloketenes have been described. Thus, exposure of a THF solution
of Cp 2 Sm(THF) 2 to an atmosphere of carbon monoxide resulted in the smooth formation of the
ketene carboxylate (44) <85JA3728>. Treatment of ((Bu'3Si)3TaCO)n in a similar manner facilitated
the formation of the moderately stable ketene (45) <89JA9057>, while the reaction between
Cl2W(PPh2Me)4 and carbon suboxide leads to the ketene (46) baring both tungsten and phosphorus
substituents <88JA4855>.
Perhaps more useful is the observation that, when the tungsten, molybdenum or chromium
complexes (47) were exposed to an atmosphere of carbon monoxide, the stable silyl ketene (48) was
furnished in reasonable yield (Equation (17)) <89JOM(373)203>. Similarly, treatment of chromium
carbene complexes, for example, (49) with bistrimethylsilylacetylene, provided the vinylogous silyl-
ketenes (50) and (51), in useful quantity (Equation (18)) <79AG(E)954>.
(17)
(18)
(19)
546 Ketenes, Cumulenes and S, Se and Te Analogues
3.16.2 THIOKETENES
Thioketenes are considerably less stable than ketenes, due in part to less efficient Tt-orbital overlap
between the carbon and the sulfur atom. This is compounded further by a tendency for these
materials to form dimers and higher oligomers (Equations (20) and (21)). An unfortunate conse-
quence of this is that many early reports detailing the preparation of thioketenes, including the first
claimed synthesis <1877CB70l, 88T1827), were in error <189OCB1571,88T1827>.
(20)
(21)
As with ketenes, the stability of this functional group is greatly influenced by the nature of any
substituents. Highly congested thioketenes such as di-/-butylthioketene are stable indefinitely at
ambient temperature, whereas the parent compound H 2 C = C = S dimerises when warmed above
— 200°C! <(88T1827>. Electronic factors also play an important role with silicon, phosphorus and
trifiuoromethyl substituents imparting a clear stabilising influence on the system. In general,
however, the synthesis of thioketene monomers is difficult, and requires the use of techniques
such as flash vacuum pyrolysis, matrix isolation or careful generation and characterisation at low
temperature. It is therefore wise to treat thioketenes as transient species, to be prepared in situ for
most synthetic purposes. For that reason the authors again highlight those processes which have
resulted in the isolation and characterisation of thioketenes, alongside those for which it is reasonable
to assume their intermediacy.
The interested reader is directed to a series of invaluable overviews. Of particular note are two
early articles by Borrmann <68HOU(7/4)312> and Mayer and Krober <75ZC91>, respectively, which
critically evaluate many of the pioneering studies. Two later articles by Schaumann <85HOU(El 1)233,
88T1827) are especially noteworthy since they provide a detailed and learned account on all aspects
of thioketene chemistry, and give a most valuable insight into this curious functional group.
(22)
Interestingly, when r-butylcyanoketene was treated with triphenylphosphine sulfide, the reaction
profile indicated the presence of a thioketene intermediate. This has yet to be rigorously established,
with spectroscopic analysis failing to detect the presence of a thioketene <7OJA4132, 71JA2812).
Triphenylphosphoranylidenethioketene, on the other hand, has been prepared from the cor-
Thioketenes 547
responding ketene through the action of carbon disulfide <(68JA3842>; and when this material is
added to electron-deficient alkynes a (2 + 2)-cycloaddition, electrocyclic ring opening sequence is
initiated that provides access to cumulated thioketenes (Scheme 51) <75AG(E)53>.
Scheme 51
Scheme 52
Scheme 53
Scheme 54
One important extension to these studies has shown that trimethylsilylalkynyl sulfides readily
rearrange to the corresponding trimethylsilylthioketenes under thermolysis or by the action of a
Lewis base (Scheme 55). Moreover, silylalkynyl sulfides display considerable 'thioketenoid' character
in their reactions. For example, the addition of methanol to trimethylsilylethynyltriethylsilyl sulfide
first provides trimethylsilylthioketene <77JOM(127)Cl>, which may then be quenched by a further
equivalent of methanol <76CC1008, 77RTC179, 78ZOB2137, 80CB3024, 83CB66, 83CB509, 84AG(E)439>.
Scheme 55
With alkynylallyl sulfides the thia-Cope rearrangement is also facile, providing a ready access to
allylthioketenes (Equation (23)) <68RTC1236, 74CB3562, 77TL4307, 79LA1746>. Similarly, thermolysis of
alkynylpropargyl sulfides <74RTC26,79RTC55) and alkynylallenyl sulfides <72RTC578> can be readily
accomplished thereby providing access to allenic and propargylic thioketenes respectively (Equa-
tions (24) and (25)).
Thioketenes 549
(23)
(24)
(25)
Scheme 56
(26)
Several other alkeneation procedures have been extended towards reaction with carbon disulfide,
albeit in less detail. The use of the Peterson protocol (Scheme 57) <88TL1827> and of sulfur ylides
(Scheme 58) <71T1781> to effect construction of the carbon to carbon double bond have also been
reported, but the true effectiveness of these methods has yet to be fully determined. For completion,
the conversion of P h 3 P = C = C = O to P h 3 P = C = C = S by the action of carbon disulfide should also
be mentioned <68JA3842>.
Scheme 57
Scheme 58
550 Ketenes, Cumulenes and S, Se and Te Analogues
Another conceptionally simple approach to thioketenes is through the union of a carbenoid
species and carbon monosulfide. Unfortunately, this process has proven to be of limited use
<9UOC1317> owing to the readiness with which most thioketenes undergo [3 + 2] cycloaddition
reactions with diazo complexes (see Scheme 61) <70JOC3470>.
Scheme 59
(27)
Scheme 60
are also noted here, as the intermediacy of diazetinethiones and thiaphosphetanes, respectively,
have been implicated in these processes <91JOC1317> (Scheme 61).
Scheme 61
Scheme 62
One of the most important routes to thioketenes involves the extrusion of nitrogen from 1,2,3-
thiadiazoles <77AG(E)835> which leads to the generation of a Wolff-type intermediate that may
undergo rearrangement to a thioketene <58LA(614)4, 71T5953). Several methods have been described
552 Ketenes, Cumulenes and S, Se and Te Analogues
to accomplish this transformation, including the use of thermolysis (20HCA833, 77T449, 87CC573),
photolysis <85LA(614)4> and, needless to say, flash vacuum pyrolysis <75AG(E)248,77CB1225,79LA1734).
Of these techniques, the former and the latter have found most favour since they are less prone to
side reactions (Scheme 63).
Scheme 63
Nitrogen extrusion from 1,2,3-thiadiazoles can also be brought about by treatment with alkyl
lithium reagents (66RTC889, 68RTC38, 77S888, 79CL535). This procedure is believed to proceed via the
lithium alkynyl thiolate (Scheme 64), the chemistry of which has been discussed in Section 3.16.2.4.
Scheme 64
The intermediacy of carbenoid species has been implicated in several other thioketene syntheses.
For example, flash vacuum pyrolysis of 2-mercaptoaryloic acid derivatives is believed to give
rise to thioketenes via sequential dehydration to the jS-thiolactone, loss of carbon monoxide and
rearrangement of the carbenoid precursor (Scheme 65) <83AG(E)543>. l,3-Dithiolen-2-thiolones
<79NJC149> and isothiazoles <77JA4842> also suffer elimination, of carbon disulfide and hydrogen
cyanide, respectively, to give first carbenoid intermediates which rearrange to thioketenes. The
photochemically induced extrusion of carbon monoxide from l,3-dithiolen-2-ones, on the other
hand, leads to an unstable a-dithione which then equilibrates to the corresponding mer-
captothioketenes (Scheme 66) <82NJC40l>. 1,2-Dithiolene-3-thiones <74CB502> and isothiazol-5-
thiones <85CB85l> have also been transformed into thioketenes through phosphine-induced desul-
furisations, while l,2-dithiolen-3-ones <75LA1513> and 3-isothiazolthiones <70T1493>, each suffer
decomposition in the presence of base with the formation of thioketene dimers.
Scheme 65
Scheme 66
(28)
3.16.3 SELENOKETENES
Very few selenoketenes have been reported, and access to this curious functional group has
generally followed analogous procedures towards thioketenes. Thus, a variety of 1,2,3-selenodiazoles
have been converted into the corresponding selenoketene by thermolysis <79CC99> or photolysis
(Equation (29)) <72TL445, 76JA7872, 77JA4842). Similarly, the thermally induced rearrangement of
benzo-l,2,3-selenodiazole (Equation (30)) <80AG(E)69> and the seleno-Cope rearrangement of vari-
ous allyl butynyl selenides have provided routes to selenoketenes, albeit transiently (Equation (31))
<79RTC55, 80TL4251). In addition, a [3 + 2]-cycloaddition reaction between a transient selenoketene
and its anion has been postulated in the base-catalysed conversion of 4-aryl-1,2,3-selenodiazoles
into diselenofulvenes (Scheme 67) <73JOC338, 74JOC3906). Phenylselenoketene has also been invoked
as an intermediate in the reaction between bis(dimethylaluminium)selenide and the ketene silyl
acetal (55), on the basis that the adduct (56) was obtained (28%) when the reaction was performed
in the presence of cyclopentadiene (Scheme 68) <92TL7865>.
(29)
(30)
(31)
Scheme 67
554 Ketenes, Cumulenes and S, Se and Te Analogues
Scheme 68
Transition metal complexes of selenoketenes are usually considerably more stable than the parent
compound. Indeed, by analogy with thioketenes these may be synthesised by the addition of selenium
to vinylidene transition metal complexes <91OM3967>. Again, a method of liberating the monomer
from the metal centre has yet to be described. Finally, it is necessary to note that a Chemical
Abstracts Service on-line search failed to reference any example of a telluroketene (R 2 C=C=Te).
Whether such compounds can be prepared is a matter for speculation; however, their use in synthesis
would surely be limited.
Copyright # 1995, Elsevier Ltd. All R ights Reserved Comprehensive Organic Functional Group Transformations
3.17
Ketenimines and Their P, As, Sb,
and Bi Analogues
JOSEPH P. MICHAEL and CHARLES B. DE KONING
University of the Witwatersrand, South Africa
2[06[0 KETENIMINES AND THEIR DERIVATIVES "R1C1C1NH"R#\ ETC[# 444
2[06[0[0 Introduction 444
2[06[0[1 Ketenimines from Precursors Containin` the CCN Triad 445
2[06[0[1[0 By elimination reactions 445
2[06[0[1[1 By elimination reactions accompanied by skeletal rearran`ement 452
2[06[0[1[2 From alkanenitriles\ their a!anions or their a!radicals 454
2[06[0[1[3 By cleava`e of heterocyclic compounds 463
2[06[0[1[4 From other ketenimines 479
2[06[0[1[5 By miscellaneous pericyclic processes 471
2[06[0[2 Ketenimines from "CC¦N# Precursors 473
2[06[0[2[0 From ketenes "or related precursors# and iminophosphoranes "or related precursors# 473
2[06[0[2[1 From haloalkenes or haloalkynes and amines or amine derivatives 477
2[06[0[3 Ketenimines from "C¦CN# Precursors 480
2[06[0[3[0 From phosphorus ylides and isocyanates or related compounds 480
2[06[0[3[1 By alkylation of isocyanides 482
2[06[0[3[2 Formal cycloaddition processes 599
2[06[0[4 Keteniminium Salts 590
2[06[0[0 Introduction
Ketenimines "IUPAC name] 0!alkenylideneamines# are comparative latecomers to organic chem!
istry\ the _rst stable member of the group having been reported by Staudinger in 0808 ð08HCA524Ł[
Their relatively recent discovery and continuing rarity re~ect the susceptibility of the C1C1N unit
to decomposition by hydrolysis\ dimerization\ and polymerization\ amongst other reactions[ In
general\ hydrogen!substituted ketenimines and those with small unbranched alkyl substituents are
elusive substances[ For example\ the simplest ketenimine\ H1C1C1NH\ was _rst isolated in an
argon matrix at 3 K ð52JA167Ł[ Although longevity\ and hence synthetic signi_cance\ is conferred
445 Ketenimines and P\ As\ Sb\ and Bi Analo`ues
by substituents that stabilize the 0!azaallene core either electronically or sterically\ many ketenimines
that do not survive puri_cation are stable for limited periods at low temperature or in solution[
Ketenimines also play a role as discrete but transient intermediates in many interconversions\
especially in eliminationÐaddition processes and in the formation of heterocyclic systems[ The
selection of material for this chapter has thus been complicated by the hazy distinction that exists
between unstable but spectroscopically characterizable ketenimines\ and ephemeral species produced
by methods that nonetheless have synthetic value[
The inherent axial dissymmetry of the formal C1C1N unit means that appropriately substituted
ketenimines should\ in principle\ be obtained in two enantiomeric forms[ However\ such enantiomers
have never been isolated\ though ketenimine diastereomers have been detected in one highly spe!
cialized case ð70CL416Ł[ Inversion at nitrogen appears to constitute the principal mechanism for
racemization\ and spectroscopically determined barriers to racemization for a substantial number
of ketenimines are in the range 29Ð52 kcal mol−0 "015Ð153 kJ mol−0# ð70CB2640\ 73T782Ł[ In fact\ the
description of ketenimines as 0!azaallenes "0a# may well be an oversimpli_cation[ Other feasible
canonical forms include a zwitterionic form "0b# highlighting the nucleophilicity of the b!carbon
atom\ and an alternative zwitterion "0c# in which the electrophilicity of the central carbon atom is
emphasized "Scheme 0#[ Single!crystal x!ray di}raction studies have con_rmed the approximately
linear "069Ð065># nature of the CCN triad\ but several examples "e[g[\ with R0 R1 MeSO1# in
which a linear C1N
0R2 angle is apparent point to a large contribution from the canonical form
"0b# ðB!79MI 206!90\ 78AX"C#371Ł[ The pronounced shielding of the terminal allenic carbon "dC 26Ð67
ppm for various methyl! and phenyl!substituted ketenimines# also suggests the conjugative inter!
action between the C1C bond and the nitrogen lone pair implicit in the canonical form "0b#
ð64CL40Ł^ and a similar conclusion can be drawn from up_eld 04N chemical shifts ð70OMR"06#079Ł[
–
R1 R3 R1 R1 N R3
– +
• N N R3
+
:
R2 R2 R2
(1a) (1b) (1c)
Scheme 1
The _rst review dealing with the synthesis and reactions of ketenimines was published in 0857\
and contained experimental procedures for preparing representative compounds ð57HOU"6:3#212Ł[
Subsequent reviews by Krow ð60AG"E#324Ł and by Barker and McHenry ðB!79MI 206!91Ł also
included structural and spectroscopic properties of ketenimines[ Specialized reviews by Gambaryan
ð65RCR529Ł and Aumann ð77AG"E#0345Ł cover the topics of ~uorinated ketenimines and metal
complexes of ketenimines respectively[ A very thorough review of post!0857 ketenimine chemistry
has appeared in the Houben!Weyl series ð82HOU"E04:2#1420Ł[
(2)
Scheme 2
The Bestmann method lends itself to the synthesis of ketenimines bearing heteroatomic sub!
stituents on carbon[ For example\ But"Br#C1C1NBut has been obtained from the corresponding
a!bromo amide in 39) yield ð63JOC378Ł\ and C!phosphoryl ketenimines\ "EtO#1PO"R0#C1C1NR1
"R0 Me\ Ph^ R1 Et\ Ph#\ were made by the standard procedure in yields of 58Ð82) ð68CC899\
79JOC4274\ 80S0052Ł[ Bestmann and Lehnen have even succeeded in making a bis"phosphoryl# keten!
imine\ ð"EtO#1POŁ1C1C1NPh\ as a comparatively stable\ distillable liquid "76) yield# ð80TL3168Ł[
The C!sulfenyl ketenimines "R0S#R1C1C1NR2 "R0 Me\ Ph^ R1 Me\ Et\ Pri^ R2 Et\ Ph# have
been prepared in yields of 42Ð52) ð70JCS"P0#1616Ł\ and the sulfone PhSO1C"Me#1C1NEt was
also accessible in 28) yield if re~uxing 0\1!dichloroethane was used as the solvent ð80S0052Ł[
A potentially valuable modi_cation of the Bestmann procedure uses 1) cross!linked polystyrene
as a support for the phosphine ð79MI 206!92Ł[ The e}ective reagent is poly"styryldiphenylphosphine
dibromide#\ which\ when used with triethylamine in re~uxing benzene\ gave high yields "69Ð89)#
of trisubstituted ketenimines from secondary amides[ Polymeric phosphine oxide was easily
447 Ketenimines and P\ As\ Sb\ and Bi Analo`ues
Table 1 Representative ketenimines\ R0R1C1C1NR2\ prepared by dehydration of secondary amides\
R0R1CHCONHR2\ with dibromotriphenylphosphorane[
Ð*ÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐ
Entry Ketenimine Method a Yield Ref[
")#
ÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐ
*
0 Ph1C1C1N"C5H3R# "RH\ o!Me\ p!Me# i 79Ð74 57LA"607#13
1 Ph1C1C1NBun i 53 57LA"607#13
2 R1C1C1NPh "RMe\ EtO1C# i 34\ 49 57LA"607#13
3 0\3!"Ph1C1C1N#1C5H3 i 24 63JHC522
4 H1C1CH"Me#C1C1N"p!C5H3Me# i 34 62JA4306
5 H1C1CHCH1C1N"p!C5H3Me# i Ð 71JOC2887
6 PhCH1C1NR "RMe\ c!C5H00\ Ph\ 1\3\5!C5H1Me2# ii 54Ð74 79JOC2655
7 MeCO"R#C1C1NPh "RMe\ Et\ Pri# iii 39Ð49 62TL4056
8 EtO1C"R#C1C1NPh "RMe\ Et# iii 79\ 65 62TL4056
09 NC"Me#C1C1NEt iv 10 80S0052
00 "C5Me4#1C1C1NBn i 51 81JOC251
01 Me1C1C1NSO10p!Tol i b 79TL2970\ 71TL1898
ÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐ
*
a
PPh2\ Br1\ NEt2^ solvents and temperatures are as follows] i\ CH1Cl1\ re~ux^ ii\ CCl3\ re~ux^ iii\ C5H5\ ³09>C^ iv\ ClCH1CH1Cl\ RT[
b
Characterized spectroscopically[
Ph
O Ph
CN
N N
N •
Me
• Ph
O
Ph
O O MeO2C
N
Me
(3) (4)
removed by _ltration\ after which the phosphine could be regenerated by reduction with tri!
chlorosilane[
A di}erent variation uses dichlorotriphenylphosphorane\ prepared in situ from triphenylphos!
phine and tetrachloromethane\ for generating trisubstituted "mostly triaryl# ketenimines from
amides in yields of 44Ð76) ð66ZC82Ł[ This combination of reagents has also been used for the
synthesis of imino ketenimines by formal 0\3 elimination from 2!aminoacrylamides "Equation "0##
ð61TL0408Ł[
EtO2C EtO2C
CONHBut Ph3P/CCl4, NEt3, CH2Cl2, RT • NBut
(1)
R1HN R1N
R2 R2
R1 R2 Yield (%)
Ph Me 54
Ph Ph 61
2,6-C6H3Me2 Me 69
O Cl
PCl5, C6H6 NEt3
R1 R3
R1 R1
NHR3 NR3 • N
R2 R2 R2
Scheme 3
The imidoyl chloride method is suitable for the preparation of ketenimines bearing chiral sub!
stituents on nitrogen^ for example\ compounds "4#Ð"8# were obtained from secondary amides via
imidoyl chlorides in yields of 61Ð099) ð74CPB1220\ 74CPB3580Ł[ More unusual ketenimines include
the penicillin derivatives "09a# and "09b#\ prepared in a 8 ] 0 ratio "69) yield# from an epimeric
mixture of the corresponding imidoyl chlorides ð63TL0404Ł[ The 5!deutero analogue of "09a# was
accessible from the imidoyl chloride on treatment with triethylamine and deuterium chloride
ð63TL0404Ł[ Similar reactions have been demonstrated for cephalosporins ð65CC405\ 66GEP"O#1617773Ł[
By contrast\ treatment of penicillin derivatives such as "00# with phosphorus pentachloride and
pyridine in benzene gave the ketenimine "01# directly^ no intermediate imidoyl chloride was detected
"Equation "1## ð66TL2720Ł[
Et
R2
• N R2
R1 • N
R1
(5) (6)
R1 R2 R1 R2
H Ph Me Ph
Me Ph Et Ph
Et Ph H2C=CHCH2 Ph
CH2=CHCH2 Ph Et o-C6H4OMe
Et o-C6H4OMe
OMe Ph
• N
Ph R Ph
Et H
• N • N
Et Et
(7) (8) (9)
R = Me, Pri, Bn
Ph Ph
• N H • N H
S S
6
N N
O O
CO2CH2O2 CBut CO2CH2O2CBut
(10a) (10b)
Ph Ph
H H H
N • N
S PCl5, pyridine, C6H6, 5 °C S
PhO2C PhO2C (2)
O N 85% N
O O
O O
O NO2 O NO2
(11) (12)
459 Ketenimines and P\ As\ Sb\ and Bi Analo`ues
Table 2 Representative ketenimines\ R0R1C1C1NR2\ prepared from secondary amides\ R0R1CHCONHR2\
via imidoyl chlorides\ R0R1CHC"Cl#1NR2[
Ph
6 • NPri (R = H, D, Me) i, then iii 34–50 80JCS(P2)579
R
BnMe2C
7 • NR (R = Bun, Bus) i, then v 85, 61 81CB3751
BnMe2C
81CB3751
8 • N(C6H4R) (R = H, p-Me, p-F, p-Cl, p-Br, i, then v 22–87
84T893
But
12 i, then iii 54–64 86CB3411
• N(p-C6H4R) (R = H, Me, OMe, Cl, NO2)
C6Me5
13 • NCHPh2 vii 30 92JOC362
C6Me5
O N(c-C6H11)
•
14 N i, then viii b 80TL3081
O
Ph
15 • NOEt i, then ix c 92BAU2039
a i, PCl /C H , reflux; ii, Et N/Et O, RT; iii, Et N/C H , reflux; iv, Et N/C H Me, 110 °C; v, Et N/Et O, reflux; vi, KOBut/THF, 0 °C;
5 6 6 3 2 3 6 6 3 6 5 3 2
vii, SOCl2/pyridine, RT; viii Et3N, CHCl3, reflux; ix, NaH, 18-crown-6, THF, reflux. b Not reported. c Ph(Me)C(OEt)CN was isolated (58%).
Ketenimine formation from imidoyl halides other than imidoyl chlorides is rare[ Elimination of
hydrogen ~uoride from imidoyl ~uorides with powdered potassium hydroxide in ether has been
used for preparing bis"tri~uoromethyl# ketenimines\ "F2C#1C1C1NR "Raryl\ alkyl\ cycloalkyl#\
in yields of 47Ð89) ð62BAU0639Ł[ The preparation of the ketene hydrazone "F2C#1C1C1NNMe1
Ketenimines 450
by this method "34) yield# has also been claimed ð62BAU0639Ł[ Imidoyl bromides are the presumed
intermediates in the rearrangementÐelimination reaction to be described in Section 2[06[0[1[1"i#
below[
O Cl
R1 R3
R1 PCl5, C6H6, heat R1 NaI, Me2CO, heat
NHR3 NR3 • N
R2 R2 R2
Cl Cl
Scheme 4
Few improvements to the original reaction conditions have been reported[ Lithium amalgam in
ether o}ers advantages over sodium iodide in acetone for preparing the bis"ketenimine# "02# from
the corresponding bis"dichloro# precursor "50) versus 12) yield# ð54JOC2607Ł[ Various triaryl
ketenimines\ including N!"p!nitrophenyl#diphenylketenimine\ have been obtained from a!chloro
imidoyl chlorides in yields of 46Ð80) by dechlorination with copper powder in re~uxing benzene
ð58JCED397Ł[ Ethylmagnesium bromide is the reagent in the unique dehalogenation shown in
Equation "2# ð68LA72Ł[
Me Me
N EtMgBr, Et2O N
–106 °C to –60 °C But
But + But (3)
Cl • NMe
Br Br
22% 66%
Cl Cl
• •
N N
Cl Cl
(13)
R S R
PriN • NPri/AcCl, NEt3, CH2Cl2,
Cl • N
H
X N N Y or NMe, CH2Cl2 X N
H Ph
(4)
X X
(14) Scheme 5
CO2Et
• CO2Et
N
N
EtO2C •
CO2Et
(15)
The reaction of imino thioesters with organometallic reagents produced ketones by a pathway in
which ketenimines have been postulated as intermediates ð77BSF772Ł[ When the silylated imino
thioether "05# was treated with n!butyllithium and one equivalent of allyl bromide "present to
intercept the expelled methanethiolate anion#\ the disubstituted ketenimine "06# "RH# was isolated
in a remarkable 72) yield via an N!lithiated enamine "Scheme 5# ð80JCS"P0#2278\ 80PS"48#030Ł[ With
two equivalents of base and of haloalkane\ compound "06# "RH# apparently underwent C!
lithiation followed by alkylation^ the ketenimines "06# "RMe\ Et\ Bn\ allyl\ crotyl# were obtained
in 44Ð63) yields[ Alternative but related routes to less stable ketenimines "characterized only by
low!temperature IR and 02C NMR spectroscopy# involved "i# ~ash vacuum thermolysis of the N!
silyl enamine "07#\ which yielded N!phenyl!C!methylketenimine after expulsion of TMS!SMe\ and
"ii# direct ~ash vacuum thermolysis of the imino thioether "05#\ which gave N!phenylketenimine
itself ð80PS030Ł[
TMS Ph
N
SMe
(18)
The same product was formed in moderate yield by sequential treatment of N!"t!butyl#!2\2!di!
methylbutyramide "10# with n!butyllithium\ benzenesulfonyl chloride\ and again n!butyllithium
ð68AG"E#677Ł[ The synthesis of 0\2!diketones from N!phenylacrylimidates and Grignard reagents
probably also involves ketenimine intermediates that result from conjugate addition followed by an
elimination akin to that shown in Scheme 6 ð74CC0662Ł[
But i, BunLi
N MeLi, Et2O, or But O
ButLi, hexane ii, PhSO2Cl
But • NBut But
OMe iii, BunLi NHBut
(20)
(19) (21)
Scheme 7
a!Cyano enamines "11# underwent elimination of hydrogen cyanide when treated with methyl!
magnesium iodide in ether^ trialkyl ketenimines were isolated in yields of 16Ð50) ð67JOC1569Ł[
Yields were improved to 44Ð77) when methyllithium was used as the base ð71OPP102Ł[ Imidoyl
cyanides "12#\ which are structural isomers of "11#\ can be prepared by N!chlorination:
dehydrochlorination of a!aminonitriles^ they lose hydrogen cyanide when passed in the gaseous
phase over solid potassium t!butoxide heated to 009>C ð76JOC0036Ł[ The products\ C!unsubstituted!
and C!monomethyl!N!alkyl ketenimines\ were isolated "59Ð54) yields# by condensation on a cold
_nger\ and were stable for several days in solution[
R3
HN N R2
R1 R1
CN CN
R2
(22) (23)
R1, R2 = Me, Et; R3 = Pri, But R1, R2 = H, Me
Bn N OH Bn Cl Bn
PPh3, CCl4, NEt3 •
Bn 80 °C N N
54%
Bn Bn
(24) (25) (26)
Scheme 8
R R
• N
+
:N N N
–
R
R
N :N:
Scheme 9
EtO2C C6H6, hν EtO2C EtO2C Me
(253 nm)
+ • N (5)
R
R N3 93% N R
(27) 3:1 (28)
Ketenimines 454
Et Et Et
c-C6H12, hν • NH CN
(EtO)2P N3
+
(EtO)2P (EtO)2P
O O O
30% 7%
Scheme 10
The related photochemical decomposition of aryl azides via singlet nitrenes and thence ring
expansion to unstable but trappable cyclic ketenimines such as "18# "Scheme 00# has been reviewed
ð81MI 206!90Ł[ The much slower ring expansion of 1\5!di~uorinated phenyl azides during laser ~ash
photolysis suggests that ready interception of the nitrenes may make the compounds useful as
photoa.nity labels ð82MI 206!90Ł[
: :
N3 N N
hν
(29)
Scheme 11
R1 R1 R1
– +
N • NH NH
R2 R2 R2
(30a) (30b) (30c)
Scheme 12
hν (254 nm)
c-C6H12, 96 h
Ph NMe2 • NMe N
Ph Ph
Scheme 13
In the reaction shown in Scheme 03\ direct alkylation of nitriles by the t!butyl cation yields
nitrilium ions "23# that are subsequently deprotonated with organic bases "triethylamine or N!"t!
butyl#!N?\N?!pentamethyleneisobutyramidine# to give N!"t!butyl# ketenimines in fair yields
ð77JOC07Ł[ This mild procedure provides access to the C\C!disubstituted ketenimines
R1C1C1NBut"RPh\ 62)^ RMe\ 4)#\ the C!monosubstituted ketenimines RCH1C1NBut
"RMe\ Et\ Prn\ Bun\ Ph\ CO1Et\ vinyl\ 29Ð79)#\ the very labile ClCH1C1NBut "19)#\ and the
C!unsubstituted compound H1C1C1NBut "14)#\ reputedly the smallest member of the ketenimine
family to be isolated on a preparative scale[
Scheme 14
R1 R1
– N • N– (7)
R2 R2
(35) (36)
R1 R2 Yield
Ph Ph 60%(20:80)
Ph Me 65%(25:75)
Ph Et 55%(30:70)
Bn Bn 85%(32:68)
CO2Me CN
R1
• NR2 •
Fe NH Fe NH2 Fe
N
SMe
(37) (38) (39)
R1 = 2,4,6-C6H2Me3, R2 = But
R1 = Ph2C(Me), R2 = 2,6-C6H3Me2
Silylation on nitrogen represents the most generally useful way of exploiting a!anions of alkane!
nitriles as precursors for ketenimines[ For example\ trimethylsilylation of the acetonitrile anion has
been shown to yield the remarkably stable C\C\N!tris"trimethylsilyl#ketenimine "30# ð45JA1163Ł\ not
457 Ketenimines and P\ As\ Sb\ and Bi Analo`ues
PPh3
+ N
N N PPh3
Ph Ph Ph N
• Ph Ph
Ph Ph •
PPh3, Br2, NEt3 Br– (40), NEt3
Ph
O O O O O N O
N N 76% O O
N
Me Me Me
Me
(40)
Scheme 15
via a trianion as was once thought ð52AG"E#506Ł\ but by sequential deprotonation and progressive
silylation ð60JA0603Ł[ The speci_c case shown in Scheme 05 also demonstrates the concurrent
formation of a trisilyl ynamine "31#\ which rearranged quantitatively to the ketenimine "30# on
heating at 059>C ð60JA0603Ł[ In silylation\ as in alkylation\ steric factors play a signi_cant role in
swinging the reaction towards N!silyl ketenimines rather than a!C!silyl alkanenitriles ð81JOC0839Ł[
Variations in the nature of the substituents on the acetonitrile framework\ in the base\ and in the
silylating agent have been explored\ and Table 3 gives an indication of some of these variations[
The silylation of cyanohydrin anions "entries 01 and 02# is particularly interesting because it provides
access to ketenimines with oxygen substituents on the carbon terminus ð81JOC0191Ł[
160 °C
Scheme 16
Ketenimines bearing transition metal substituents on nitrogen may be prepared by treating salts
of cyanoform with suitable metal complexes\ followed by ligand exchange if necessary[ Spectro!
scopic studies "especially IR# have provided good evidence for C0N s bonding in the follow!
ing keteniminato complexes] "NC#1C1C1NM"PR2#"NO#1 "MCo\ Ni^ RPh\ c!C5H00#
ð55ZAAC"233#174Ł^ "NC#1C1C1NFe"CO#1Cp and "NC#1C1C1NM"CO#4−NEt3¦ "MCr\ Mo\
W# ð56JOM"7#436Ł^ trans!"NC#1C1C1NPt"H#"PPh2#1\ cis!"NC#1C1C1NPt"X#"PPh2#1 "XCl\ Et#\
and "NC#1C1C1NIr"CO#"L#"PPh2#1 "LSO1\ TCNE\ fumaronitrile#\ amongst othersð61JOM"28#106Ł^
trans!"NC#1C1C1NM"CO#"PPh2#1 "MIr\ Rh# ð61JOM"28#106\ 62CB1033Ł^ "NC#1C1C1NM
"CO#2"PPh2#1 "MMn\ Re# and polymeric "ðNCŁ1C1C1NMðCOŁ2#n ð62CB1033Ł[ A similar reaction
has been demonstrated with some main group metals\ and the complexes "NC#1C1C1NSnPh2\
"NC#1C1C1NPbPh2 and "NC#1C1C1NTlPh1 have been characterized by IR spectroscopy
ð56ZAAC"243#58Ł[ Reaction of methyl cyanoacetate with hydroxoplatinum complexes\ Pt"OH#PhL1
"Lphosphine#\ similarly gave keteniminato complexes of the form MeO1CCH1C1NPtPhL1
ð79JOM"088#008Ł[
TMS TMS
1 MeCN NaN(TMS)2, TMS-Cl • N 63AG(E)617
TMS
Ph TMS
2 PhCH2CN NaN(TMS)2, TMS-Cl • N 63AG(E)617
TMS
Ph TMS
3 Ph2CHCN NaN(TMS) 2, TMS-Cl • N 63AG(E)617
Ph
RMe2Si SiMe2R
• N
4 MeCN ButLi, RMe2SiCl RMe2Si (R = H, Me, But) 71JA1714
+ RMe2Si N(SiMe2R)2
Ph SiR3
5 PhCH2CN NaH/DME, R3SiCl • N 83–94 73CR(C)1803
Ph (R = Me, Et, Prn)
ButMe2Si SiButMe2
• N
6 RCH2CN LDA, ButMe2SiCl 98–100 74SC127
R
(R = Me, Et, Prn, n-C6H13, H2C=CH)
Ph Ph SiButMe2
7 CN LDA, ButMe • N 74JOC2799
2SiCl 73–94
R R 83JOC4087
(R = Me, Et, Pri, n-C8H17, Ph)
TMS TMS TMS
8 MeCN TMS-OTf, Et3N • N + TMS CN 73 (56:43) 77S636
TMS TMS
(Pri)3Si Si(Pri)3
9 CN LDA, (Pri)3SiCl 77 87TL397
• N
CN TMS
11 LDA, TMS-Cl • N 86 90CB2339
TMS-O TMS
12 TMS-OCH2CN LDA, TMS-Cl • N 75 92JOC1202
TMS
TMS-O TMS-O TMS
13 CN LDA, TMS-Cl • N 81 92JOC1202
Pri Pri
C6Me5 C6Me5 SiButMe2
14 CN BunLi/TMEDA, • N 92JOC1940
C6Me5 ButMe2SiCl C6Me5
469 Ketenimines and P\ As\ Sb\ and Bi Analo`ues
O
Ph P(OEt)3 Ph Ph Ph P(OEt)2
C6H6, ∆ + +
–
Cl N N ClP(OEt)3 • NP(OEt)3 Cl– • N
91%
Ph Ph Ph Ph
(44) (45) (43)
Scheme 17
sul_nates gave yet another variation of the Perkow reaction\ a}ording the N!sulfonyl ketenimines
"37# in yields of ½39) ð61CR"C#0298Ł[
O
P(OMe)2
O
R1 CO2Et R1 CO2Et R1 OEt
P(OMe)3, C6H6, 0 °C
R2 CN R2 + R2 (9)
NC Br NC • O NC
N P(OMe)2 N
(46) (47)
R1 = R2 = Ph 85 15
R1 = R2 = Bn 80 20
R1 = Ph, R2 = Me 70 30
R1 CO2Et
R2 R1, R2 = Ph, Bn
NC • Ar = Ph, p-Tol
N SO2Ar
(48)
F 3C SMe
CF3
F3C SMe
• R CF3
N Sn N
• R
R R
N Sn N
R R
(49)
N NC CN
NC • UCp3
NC • Ph3P PPh3
N Ir CO
NC CN
NC CN NC
R CN
(50) (51)
F 3C CN
S
O CDCl3 O F3C CN O
N S+ S+ CN
N 40 °C CH2– CF3
–
CF3
NC
(52) (53) (56)
CF3
S S
O O
CN + CF3
N CF3 CN
•
F3 C CN
(54) 78:22 (55)
Scheme 19
Ketenimines 462
S CF3
CN
N
• CF3
(57)
NC
• N
N N
NC
CN
(60) (61)
Oxidation of hindered a!cyano acetic esters with iodobenzene diacetate in methanol gave good
yields of the dimeric ketenimines "51#\ apparently by way of the hypervalent N!iodo ketenimine
intermediates "52# "Scheme 19# ð66TL2238Ł[ These unusual intermediates are assumed to decompose
homolytically\ after which the radical fragments couple to give varying amounts of C\N! and C\C!
dimers depending on the solvent used[ IR spectroscopy provided good evidence for the intermediacy
of the N!iodo ketenimine "53# when the oxidation was performed on the cyanosuccinimide substrate
"54# "RH#^ spectroscopic evidence for the iodine!linked bis"ketenimine# "55# was adduced in the
case of the analogous N!methyl compound "54# "RMe# ð66TL2242Ł[
X MeO2C R
MeO2C PhI(OAc)2 MeO2C I Ph MeO2C CN
MeOH, 20 °C –PhI
CN • N • N
R R R
(63) (62)
R Yield (%)
Ph2C(CN) 85
Bn2C(CN) 70
Ph2CH 20
Scheme 20
Ph N OAc Ph CN Ph N N Ph
• I • I •
Ph Ph Ph Ph
Ph Ph
O O O O O O O O
N N N N
H R Me Me
(64) (65) (66)
463 Ketenimines and P\ As\ Sb\ and Bi Analo`ues
"vii# Reactions of a!cyanoalkylsulfonium salts
Ketenimines have been prepared from a!cyanoalkylsulfonium salts by two distinct pathways
according to whether the reaction partner acts as a nucleophile or as a base[ For example\ the
reaction shown in Scheme 10 commences with nucleophilic attack of the stabilized enolate "56# on
the sulfonium salt "57#[ Homolysis of the unstable sulfurane intermediate "58# produced radicals\
the recombination of which gave various dimeric products that included the ketenimine "69#
ð67TL2608Ł[ By contrast\ the same sulfonium salt "57# was converted into the sulfonium ylide
"60# on treatment with triethylamine^ rapid ð1\2Ł!sigmatropic rearrangement yielded both the N!
"methylthiomethyl# ketenimine "61# and the nitrile "62#\ the latter the result of an e}ective SommeletÐ
Hauser rearrangement "Scheme 11# ð67TL2608Ł[ Although the action of n!butyllithium on "57#
resulted in products of the nucleophilic pathway only\ other sulfonium salts have given ketenimines
from the ð1\2Ł!sigmatropic pathway with both triethylamine and n!butyllithium ð67CC163Ł[ The
reaction of stabilized enolates "63# with S\S!dialkylsuccinimidosulfonium salts "64# was more
complex\ and depended on many variables\ including time\ temperature\ and the nature of the
counterion[ Scheme 12 shows examples in which products from both the homolytic and the sig!
matropic pathways were formed simultaneously ð71T416Ł[ Other succinimidosulfonium salts "e[g[\
"65# and "66## also gave rise to unusual ketenimines "e[g[\ "67#Ð"79## ð71T416Ł\ but in general the
reactions described here were too sensitive to conditions to be synthetically useful[
MeO2C Ph MeO2C
+ THF, 20 °C
Na+ – CN + p-Tol SMe2 PF6–
NC Ph NC
(67) (68)
Ph CO2Me
Ph CN
NC Ph CN
MeO2C Me Ph
Ph • Ph
p-Tol S CO2Me N CO2Me
NC Me CN
CN
(69) (70)
Scheme 21
CO2Me
MeO2C MeO2C Me MeO2C SMe
+ NEt3 + CN
p-Tol SMe2 PF6– p-Tol S • N +
SMe
NC CH2– p-Tol
N
(68)
(71) (72) (73)
Scheme 22
N SMe2+
Cl–
O
R1 CO2Me (75)
NC – Na+
THF, CH2Cl2, < 0 °C
R2 CN
(74)
R1 CO2Me
R1 CO2Me
NC
NC R1 CO2Me
R2 • CO2Me
R2 • + NC + CN
N
N R2 CN SMe
R2
SMe
R1 CN
R1 R2 Yield
Ph Ph 60%(74:13:13)
Bn Bn 30%(80:20:0)
Ph Me 70%(97:3:0)
Ph Et 65%(95:5:0)
Scheme 23
Ph X N
NaI, Me2CO, reflux
N • X (11)
Ph 83–97% Ph
Cl Cl Ph
X = H, m-Cl, m-Me, p-Cl, p-Me
N N
• •
Ph Ph
Ph Ph
(81)
R1 R2 R2
N NEt3, MeCN, RT
R1
• N (12)
65–86% Br
Br Br
(82) R1, R2 = Ph, p-C6H4Cl (83)
N!Methylketenimine has been detected as the major product of the pyrolysis of N!chloro!
propylenimine at 319>C "Equation "02## ð76JSP"012#365Ł[
Cl 420 °C Me
N (13)
• N
O LiO MeO
LDA, THF, 0 °C (MeO)2SO2
N N N
35%
• •
(84)
(85)
PhCOCl
TMS-Cl 80%
30%
TMS-O PhCO2
N N
• •
Scheme 24
N
Ph
(86)
TMS-O
O LDA, THF, 0 °C
then TMS-Cl
N (14)
N
65%
•
(87) (88)
TMS-O
3BunLi, 3TMS-Cl
O Et2O, –55 °C
N (15)
N •
TMS TMS
(89) (90)
Ph Ph
O
Ph hν (254 nm) Ph Ph
O O
40% • NPh
N N:
Ph
:
Ph Ph
(91)
Scheme 25
NEt3, CH2Cl2
hν (254 nm), –77 °C –77 °C
O
O
O • N + I–
N
NMe Me
(92) (93) (94)
Scheme 26
Woodward|s {{reagent K|| "84#\ a zwitterionic isoxazolium salt\ was introduced in 0850 ð50JA0909Ł
as the prototype of a group of useful reagents for peptide synthesis ð69T0668Ł[ The reactivity of
these isoxazolium salts was ascribed to initial deprotonation at the unsubstituted 2 position followed
by ring cleavage to form C!acyl ketenimines "85# ð50JA0996Ł\ after which interception by a car!
boxylate yielded enol esters ð57JA0260Ł suitably activated for further attack "Scheme 16#[ Subsequent
investigations by Woodward and co!workers provided _rm spectroscopic evidence for acyl ket!
enimine intermediates ð55T"S#304Ł[ For preparative purposes\ this route is limited to relatively
stable compounds such as N!"t!butyl#benzoylketenimine and the corresponding acetyl compound\
prepared in 59) and 69Ð79) yields\ respectively\ from isoxazolium perchlorates and triethylamine
ð55JA2058Ł[ Isolable C!acyl ketenimines "86#Ð"099# have also been obtained from 3\4!disubstituted
isoxazolium perchlorates or tetra~uoroborates ð58JOC2340\ 69T0668Ł[ The rather unstable C!acyl
ketenimine "85# from reagent K itself has recently been prepared in acetonitrile solution by reaction
of the salt with triethylamine ð75JA4432Ł^ other sensitive acyl ketenimines have been intercepted by
the addition of cuprates ð78SC0928Ł[ Several isoxazolium salts bearing heteroatomic substituents have
also been shown to yield ketenimines on treatment with base[ These include the 4!aminoisoxazolium
precursor "090# of the ketenimineÐamide "091# "Equation "05## ð63CB02Ł^ and 3!azido isoxazolium
salts "092#\ from which the unique C!azido ketenimines "093#\ stable only below −59>C\ were
obtained "Scheme 17# ð72CC637Ł[
SO3– SO3–
base
O O
N+ – N+
Et Et
(95)
R
SO3– SO3– SO3– O
O– O RCO2H O
NHEt
+ • NEt
N Et
(96) O
Scheme 27
467 Ketenimines and P\ As\ Sb\ and Bi Analo`ues
O O O
R1
• NR3 • NR • NR
R2
(97) R1 = H, R2 = Ph, R3 = But, CH(Me)Ph (99) R = Me, Et (100) R = Me, Et
(98) R1 = Ph, R2 = Me, R3 = Bn, Ph, But
NH2
O
Ph NaOH, CCl4 H2N
O (16)
• NMe
N + Cl–
Ph
Me
(101) (102)
R
R ButOH, HClO4 O
NEt3, CH2Cl2
0 °C N3 –90 °C R
N3 O
O – • NBut
17–50% N + ClO4
N N3
But
(103) (104)
R = Me, Ph
Scheme 28
Isoxazolium salts may or may not be involved in the rapid transformation "Scheme 18# of N!"1!
benzoylstyryl#hydroxylamine "094a# and its hydroxyisoxazolidine tautomer "094b# to C!benzoyl!
C\N!diphenylketenimine "095#\ which was detected by IR spectroscopy ð67JCS"P0#0002Ł[ The trans!
formation can be preparatively useful\ as in the synthesis of the N!"t!butyl# analogue of "095# in
50) yield from t!butylhydroxylamine and 0\1!diphenylpropane!0\2!dione in chloroform at room
temperature ð77JOC3886Ł[
PhCO
EtOH, 5–10 °C
CHO + PhNHOH
Ph
Ph OH
Ph O PhCO
OH Ph
O • NPh
N N
Ph Ph Ph
Ph
(106)
(105a) (105b)
Scheme 29
R = Me, Ph
O
RHN
N
H
(108)
R3 R2
R1
Bu3P, CH2Cl2 R1 N
R1 N R2
N
NR4 41–87% N
S • NR4
R2 R4 R3
R3
(109) (110)
Scheme 30
p-MeOC6H4
Bu3P, CH2Cl2, 0 °C • N-p-Tol HNEt2
p-MeOC6H4
S S 66%
S N-p-Tol
(111) (112)
NH-p-Tol
p-MeOC6H4 NEt2
S
Scheme 31
R1
R1 N hν (450 W mercury lamp)
R1
N C6H6
• NPh + R2 (20)
N
R2 N
R2 Ph
Ph
(113)
R1 R2 Yield(%)
Ph Ph 60 (1:1)
H Ph 70 (3:1)
Ph H 85 (40:1)
N N2
N MeO CN
CN hν, MeOH R CN
N
N N • N
R
R CN R
(114) (115) (116)
R = H, Me, Et, 2-furyl, 2-thienyl
Scheme 32
Loss of nitrogen on gentle warming of the lithiated triazole "006# resulted in the formation of the
lithiated ketenimine "007#\ which showed a strong IR absorption at 1039 cm−0 ð60CJC0681Ł[ This
salt was trapped with iodomethane to give the ketenimine "008# and ketenimine dimer in 34) and
08) yields\ respectively "Scheme 22#[ Other electrophiles reacted at nitrogen to give ynamine
products[ However\ with aldehydes\ reaction presumably occurred at carbon\ since acrylamides
were obtained in good yield on work!up ð63LA0544Ł[
Scheme 33
But But
Ph TMS + R3MX Ph MR3
(21)
• N – TMS-X • N
NC NC
(120)
M = Ge, Sn, Pb
X = OMe, OAc
Ketenimines 470
NC Sn(But)3 NC NO
NOCl, THF, –20 °C
• N • N (23)
Ph Ph
Ph Ph
Keteniminylidene phosphoranes "010# "see Section 2[06[1[0# are able to react with various
electrophiles to yield both transient and stable ketenimines[ Examples are shown in Scheme 23
ð63AG"E#362\ 64AG"E#42Ł[ Photolysis of hexakis"t!butyl#cyclotrisilane "011# in the presence of two
equivalents of tris"trimethylsilyl#ketenimine initiated a surprising sequence of cycloadditionÐcyclo!
reversion processes\ at the end of which the novel ketenimine "012# was produced in 61) yield
"Equation "13## ð81JOM"312#218Ł[
R1
R1 R1 NPh
R2
O + Ph3P • • NPh • • NPh
R2 (121) R2
PhN PPh3
R1 R2 Yield (%)
p-C6H4NO2 H 64
Ph COPh 58
2,2'-C6H4–C6H4 75
Ketenimine!bearing penicillins\ for example "013#\ have been converted into a!methoxy ket!
enimines by addition of chlorine followed by treatment with lithium methoxide in methanol
ð66TL2720Ł[ The putative intermediate is the a!chloroimidoyl chloride "014#\ which undergoes 0\3
elimination of hydrogen chloride followed by SN? displacement of the chloride ion by methoxide
"Scheme 24#[ That similar products\ for example "015#\ can be prepared in the cephalosporin
series from preformed a!chloroimidoyl chlorides "Equation "14## lends credence to the proposed
mechanism ð65TL0296Ł[ Direct replacement of hydrogen by the methylthio group occurred on
treatment of "016# with methyl methanethiosulfonate "Equation "15## ð66TL2720Ł[
Ph H H MeO H
N S N S
LiOMe, MeOH, –78 °C •
Br N Ph N (25)
O 60% O
CO2CHPh2 CO2CHPh2
(126)
471 Ketenimines and P\ As\ Sb\ and Bi Analo`ues
H H H H
Cl
N S p-TolO2C N S
• Cl2
S N N
O Cl O
CO2p-Tol CO2CH2-p-C6H4NO2 S CO2CH2-p-C6H4NO2
(124) (125)
CO2p-Tol
MeO H
N S H
• N
S S S
N 39%
O Cl
N
CO2p-Tol CO2CH2-p-C6H4NO2 O
CO2CH2-p-C6H4NO2
Scheme 35
H H MeS H
N S N S
MeS-SO2Me, DMF, K2CO3, 0 °C
• • (26)
Ph N Ph N
28%
O O
PhO2C CO2Bn PhO2C CO2Bn
(127)
+ MeCN + Diene
NH NH
850 °C, 10–3 torr
NH
Scheme 36
NMe NMe2
Scheme 37
O H 800 –1100 °C O
CN
H2O + N + • NH MeCN
0.1–1 Pa H H
Scheme 38
Ph Ph
Ph hν R1 (28)
Ph
R1 ∆ Ph
N Ph •
R2 NR2
(129) (128)
R1 = Me, OMe, OAc
R2 = Me, Pri
Ph Ph Ph
Ph Ph
hν (mercury lamp), OAc
Ph C6H6 RT, –HOAc O
Ph Ph •
OAc 17–55%
N N R
N R
Ph
O R
O
(130) (131)
R = Me, Ph, p-C6H4X
(X = Me, OMe, Cl, NO2)
Scheme 39
Ph O O
hν (500 W mercury lamp) Ph •
C6H6
(29)
Ph N ∆ Ph •
N
(132)
473 Ketenimines and P\ As\ Sb\ and Bi Analo`ues
Ketenimines are formed as end products of the sequence of pericyclic reactions shown in Scheme
39 ð62TL2616Ł[ Equilibrium at room temperature in THF favors the azetidinoð2\1!bŁpyridine inter!
mediates "022#\ but heating in benzene induces sequential valence tautomerism\ ð0\2Ł!sigmatropic
alkyl shift\ and _nally a cycloreversion to give pyrroles "023# and the spectroscopically characterized
ketenimines "024#[ These compounds were subsequently hydrolyzed to amides\ the high isolated
yields of which "71Ð82)# re~ect the e.ciency of the entire process[
R
CO2Me R MeO2C Ph MeO2C
Ph N
N cycloaddition R N R Ph R
+ R +
MeO2C • N
MeO2C N
CO2Me Ph N Ph Ph
(134) 87–92% (135) 82–93%
( as amide)
electrocyclic cycloeversion
reaction with 1,2-H shift
R R R
Ph electrocyclic
N reaction N Ph N
MeO2C [1,3]-sigmatropic MeO2C Ph
MeO2C R C6H6, ∆ shift of R
R
THF, RT
N MeO2C MeO2C
MeO2C 73–91% N N
Ph Ph Ph R
Scheme 40
2[06[0[2[0 From ketenes "or related precursors# and iminophosphoranes "or related precursors#
The synthesis of ketenimines by the reaction of iminotriphenylphosphoranes "Ph2P1NR# with
ketenes was pioneered by Staudinger and co!workers in the early 0819s ð19CB61\ 10HCA776Ł[ Com!
pounds prepared included R1C1C1NPh "RPh\ Me\ EtO1C#\ Ph1C1C1NMe\ and
H1C1C1NPh\ the last only being stable at low temperatures[ The analogous compound
H1C1C1NEt polymerized too rapidly to be isolated[ Unfortunately\ yields of the products were
not speci_ed[
The reaction remained undeveloped for almost half a century until it was used to prepare
"CF2#1C1C1NBut "Table 5\ entry 0# ð58TL4068Ł[ A more important revival by Singer and co!
workers demonstrated that thermally labile C\C!diphenyl ketenimines\ including the _rst known
ketenimine bearing a chiral auxiliary on nitrogen\ were accessible under mild conditions and in fair
to good yields "29Ð74)# "Table 5\ entries 1Ð5# ð63CC851\ 63JOC2679\ 66JA1511Ł[ In this work\ general
reaction conditions were also clari_ed] the iminophosphoranes "generated in situ from dibromo!
Ketenimines 474
SMe
400–600 °C, 10–4 mbar SMe [1,3]-sigmatropic SMe
–CO shift of SMe
N O
O Me • NMe
• NMe
O O
(136) (138) (137)
[1,3]-sigmatropic
shift of H
O
400–600 °C, 10–4 mbar
O SMe SMe
–CO2, –Me2CO
O • •
O NHMe NHMe
O
(141)
O
O –CO2, –Me2CO
• NMe O • • • NMe
O (143)
O
(142)
Scheme 41
SMe
Ph N
O N H
•
O
(139) (140)
O O O O
R 500–700 °C RN 310 °C
O 10–4 mbar
O NMe2
10–4 mbar •
NH NH • NMe
N –Me2NH
O O NHR
O N O N O O
O
Me2NH
O • • • NR Me2N
• NR
(143) R = Me (145)
(144) R = Ph
Scheme 42
triphenylphosphorane\ a primary amine and base# reacted with ketene components "prepared in
advance or generated in situ from appropriate precursors# in inert solvents at temperatures no higher
than room temperature[ The diverse range of ketenimines subsequently made by this method
includes N!acyl ketenimines "entries 6 and 7# ð65M426\ 89CB1228Ł\ an N!cyanoalkyl ketenimine
"entry 8# ð65M426Ł\ C!phosphoryl ketenimines "entry 09# ð79JGU34Ł\ and a ~uorenylideneketenimine
"entry 01# ð70CB2640Ł[
No physical or spectroscopic data were furnished for the N!vinyl ketenimines "035#\ isolated as
viscous oils after short!column chromatography in a reaction sequence that ultimately yielded
~uorenoð1\2\3!i\ jŁisoquinolines "Scheme 32# ð89CC718\ 80JOC3997Ł[ It is of interest that an adduct
"compound "036## en route to N!vinyl ketenimines has recently been isolated from a related reaction
"Scheme 33# ð81LA04Ł[
475 Ketenimines and P\ As\ Sb\ and Bi Analo`ues
Table 5 Ketenimines\ R0R1C1C1NR2\ prepared by the reaction of ketenes\ R0R1C1C1O\ with imino!
phosphoranes\ Ph2P1NR2[
Ð*ÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐ
Entry Ketenimine Conditions Yield Ref[
")#
ÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐ
*
0 "CF2#1C1C1NBut a 58TL4068
1 Ph1C1C1NR "RBn\ But# Et1O\ 9>C 54Ð79 63JOC2679
2 Ph1C1C1NCHPh1 Et1O\ 9>C b 63JOC2679
3 "S#!"−#!Ph1C1C1NCH"Ph#"Me# Et1O\ 9>C 79Ð74 63JOC2679\ 63CC851
4 Ph1C1C1NCH1"p!C5H3R# "RCl\ Me\ OMe\ Ph# Et1O\ 9>C 29Ð59 66JA1511
5 Ph1C1C1NCH1R "R0! and 1!naphthyl# Et1O\ 9>C 29Ð59 66JA1511
6 Ph1C1C1NCOR "RPh\ "E#!PhCH1CH# C5H5\ RT a\ c 65M426
7 Ph1C1C1NCOR "ROMe\ OEt# CH1Cl1\ 9>C 65\ 79 89CB1228
8 Ph1C1C1NC"CN#Me1 C5H5\ RT a\ c 65M426\ 73T782
09 "EtO#1POC"Ph#1C1NR "RMe\ Ph# THF\ 9>C 29\ 59 79JGU34
00 Ph1C1C1NCH1!TMS C5H5\ re~ux 82 73JOC1577
01 "1\1?!C5H30C5H3#C1C1N"p!C5H3Br# Et1O\ 11>C 59 70CB2640
ÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐ
*
a b c
Yield not given[ Rearranges to Ph1CHPh1CCN[ Characterized spectroscopically[
OH
R2 OMe
OMe MeO CO2Et
• O O R2
O R1 R3
toluene, RT 150 °C N
R2 = Ph R3
R2
Ph3P • N CO2Et H
N CO2Et
R3
R1 = H, Me, Ph (146) R1
R2 = Ph, p-Tol
R3 = Et, Ph, p-Tol
Scheme 43
R
Ar Ar
• O +
R Ph3P Ph Ph
Ar –Ph3PO N
C6H6, 20 °C N
Ph3P Ph •
N R
–O
R R
R
(147)
Ar R Yield of (147) (%)
Ph Ph 77
p-C6H4Cl Ph 56
Ph 30
Scheme 44
N!Amino ketenimines "ketene hydrazones#\ notable for their rarity\ have been prepared by
Schweng and Zbiral from trimethylsilylketene and N!aziridinyl iminophosphoranes "Scheme 34#
ð65M426Ł[ The unstable products\ amongst them the unusual compound "037#\ were characterized
by IR spectroscopy[ Attempts to prepare other N!amino ketenimines from diphenylketene were
frustrated by the spontaneous decomposition of the desired products to a!amino nitriles "Scheme
35# ð65M426Ł[ A unique ketenimine azine\ Ph1C1C1N0N1CPh1\ has been prepared in 59)
yield from diphenylketene and the corresponding triphenylphosphazine ð50CB1366Ł[ Interestingly\
Staudinger had failed to isolate products from this reaction some 39 years earlier ð10HCA786Ł[
Capuano and co!workers have demonstrated that reactive ketenes\ generated in situ by a Wol}
rearrangement following the expulsion of nitrogen from 1!diazo!0\2!diketones\ may be intercepted
by iminophosphoranes "Scheme 36# ð72CB630\ 76LA072Ł[ Several of the resulting C!acyl ketenimines
"e[g[\ ArCO"Ar#C1C1N"p!Tol#\ ArPh\ p!C5H3Cl\ p!C5H3OMe# were isolated in good yield
Ketenimines 476
Ph3P N TMS
• N
N R1 • O TMS N R1
H R2 CH2Cl2 H R2
Ph Ph
R1 = R2 = H, Ph
Scheme 45
N
• N
TMS
(148)
Ph
• O Me
Ph
Me N N NC Me
CH2Cl2
N N • R Ph N
Ph3P R R = Me, 25%; Ph, 30% Ph Ph R
Ph
Scheme 46
"41Ð80)#\ while others were characterized by IR spectroscopy before conversion into various
heterocyclic products[ A similar reaction occurs with 1!diazo!2!sulfonylketones\ resulting in the
formation of C!sulfonyl ketenimines "Scheme 37# ð72CB630Ł[
N2 xylene R2 R2
100 °C, –N2 Ph3P=NR3
R1 R2 R1 R1
• •
O NR3
O O O O
Scheme 47
xylene Ph Ph
N2 100 °C, –N2 Ph3P=NAr
Ph • O • NAr
PhSO2 PhSO2 PhSO2
O
Ar Yield (%)
p-Tol 74
2,6-C6H3Me2 66
Scheme 48
Variations on the basic reaction described in this section encompass both reaction partners[ For
example\ the iminophosphorane can be replaced by the phosphoramidate anion "038#\ as reported
by Wadsworth and Emmons "Equation "29## ð51JA0205\ 53JOC1705Ł[ Ukrainian workers have similarly
prepared "EtO#1POC"Ph#1C1NR "RMe\ Ph# from sodium phosphoramidates and phos!
phorylketenes in yields of 49Ð59) ð79JGU34Ł[ Alternatively\ the ketene can be substituted by a
di}erent 0!heteroallene^ Bodeker et al[ have shown that both ketenes and ketenimines react with
N!pyridyl iminophosphorane "049# to a}ord the N!"1!pyridyl# ketenimine "040# "Equation "20##
ð79ZC100Ł[ Under the reaction conditions\ the ketenimine spontaneously dimerized to give hetero!
cyclic products[ Finally\ several ketenimines have been made by a unique method involving reaction
of bis"tri~uoromethyl#thioketene with iminosulfuranes "Equation "21## ð58USP2351378\ 61JOC0236Ł[
477 Ketenimines and P\ As\ Sb\ and Bi Analo`ues
Na+
Ph (MeOCH2)2, 20 °C Ph
–
• O + N • NR (30)
(EtO)2P R
Et Et
O
(149)
R Yield (%)
Ph 62
Bun 18
c-C6H11 58
N
C6H6 or
N Ph C6H3Me3, ∆ N
N + • X • (31)
Ph3P Ph Ph
Ph
(150) X = O or NPh (151)
F 3C CH2Cl2, RT F3C
• S + RN S NR • NR (32)
F 3C F3C
R Yield (%)
Me 17
Ph 38
Bun 20
But 48
F3C RNH2
F3C NHR F3C
base
CF2 • NR
X X F X
(152) (153) (154)
Scheme 49
Gambaryan and co!workers were the _rst researchers to investigate the reaction between per!
~uoroisobutene "041# "XCF2# and nitrogen sources[ With the iminophosphorane Ph2P1NPh\
per~uoroisobutene gave "F2C#1C1C1NPh in 23) yield ð54BAU620Ł\ while primary amines in the
presence of triethylamine similarly yielded "F2C#1C1C1NR "RMe\ 18)^ Et\ 43)^ Ph\ 86)^
p!C5H3OMe\ 78)# ð62BAU0639Ł[ The outcome of the reaction between per~uoromethacrylic esters
"044# and aniline depended on the base used^ the intermediate imidoyl ~uoride "045# and its
enamine isomer "046# were isolated in the presence of pyridine\ but ketenimines "047# resulted when
triethylamine or powdered potassium hydroxide was present "Scheme 49# ð64BAU0163Ł[ Other
workers have shown that reaction of per~uoroisobutene with the potassium salt of ben!
zenesulfonamide gave the isolable salt "048#\ from which the imidoyl ~uoride "059# and\ ultimately\
the ketenimine "050# could be produced\ as shown in Scheme 40 ð64JFC"5#116\ 65BAU462Ł^ and that
methyl per~uoromethacrylate produced MeO1C"F2C#C1C1NMe "53) yield# on reaction with
N!methylhexamethyldisilazane ð75JOU0539Ł[
The basic process has been extended to per~uoro!1!methylpent!1!ene "051# "Scheme 41#
ð63CC023Ł[ After initial displacement of ~uoride by various amines\ the putative intermediate
~uoroalkenyl imines "052# reacted with a second equivalent of amine to give C!imino ketenimines
"053#[ However\ if aromatic amines without ortho substituents were used\ the ketenimines cyclized
to 3!arylaminoquinolines[ Reaction of "051# with t!butylamine a}orded a mixture of the two
Ketenimines 478
O H
RO2C RO2C NPh RO2C
PhNH2, Et2O RO NPh
CF2 + + • NPh
F3C base F 3C F F 3C
F 3C F
(155) R = Me, Et (156) (157) (158)
Pyridine (R = Et) 48% 41% 11%
KOH (R = Et) - - 73%
NEt3 (R = Me) - - 65%
Scheme 50
KNHSO2Ph, MeCN
F 3C –40 °C to 20 °C – HCl, CH2Cl2
CF2 (CF3)2C C NSO2Ph K+
95% F 90%
F3C
(159)
F Et3N•BF3
Et2O, 20 °C
F3C
F3C SO2Ph • NSO2Ph
N
35% F3C
CF3
(160) (161)
Scheme 51
ketenimines "053# "RBut# "34) yield# and "054# "19) yield#\ perhaps because "051# isomerizes to
per~uoro!1!methylpent!0!ene ð70JFC"06#154Ł[ An analogous reaction between the sul_de!bearing
per~uoroalkene "055# and t!butylamine yielded a mixture of the ketenimines "056# and "057# and
the imidoyl ~uoride "058# "Scheme 42#[ The tetra~uoroethene hexamer "069# reacted with primary
amines to form the expected ketenimines "060# "Scheme 43#\ but piperidine\ a secondary amine\
gave an imidoyl ~uoride "061# from which limited quantities of the ketenimines "062# and "063#
could be formed on thermolysis ð74JCS"P0#1074Ł[
F3C NR
F 3C F F3C NR
RNH2
R = But • C2F5
F3C C2F5 F2C C2F5
R = 2,6-C6H3Me2 RN
(162) (163) (164)
Scheme 52
F3C F
F
• CF2CF3
ButN
(165)
(F3C)2CFS F (F3C)2CFS F
F
F3C CF(CF3)2 F2C CF(CF3)2
(166)
ButNH2, Et2O
–50 °C to 40 °C
Scheme 53
489 Ketenimines and P\ As\ Sb\ and Bi Analo`ues
F5C2 CF3 F5C2 CF3
F5C2 RNH2, Et2O F5C2
0 °C to reflux piperidine, Et2O, 18 °C
• NR CF2
F5C2 F5C2 52%
F3C F F3C F
(171) (170)
Scheme 54
There is but a single report of ketenimine production from activated chloroalkenes and amines
ð81PS"62#074Ł[ When the phosphorus!containing chloroalkene "067# was treated with primary amines\
ketenimines "068# were detected spectroscopically "Scheme 45#[ Only with t!butylamine\ however\
could the ketenimine be isolated "87) yield#[ In most cases\ the ketenimine added another equivalent
of amine\ thereby forming bisamino compounds "079#[
EtO O EtO O EtO O
RNH2, Et2O RNH2, Et2O
EtO P EtO P EtO P NHR
RT RT
CCl2 • NR
EtO P R = But, 98% EtO P EtO P NHR
EtO O EtO O EtO O
(178) (179) (180)
Scheme 56
Ketenimines may also result from the reaction of amines with chloroalkynes[ For example\
perchlorobutenyne "070# reacted with branched aliphatic primary amines\ giving the unstable but
distillable ketenimines "071# or "072# in poor yield "8Ð07)# "Scheme 46# ð79CB700Ł[ Simple primary
amines RNH1 "RPrn\ Bun\ Me1CHCH1\ c!C5H00# also apparently gave ketenimines\ but their
Ketenimines 480
formation could be inferred only by hydrolysis to amides[ A more reliable reaction between chloro!
alkynes and amines used chloroethynyl phosphonates\ "RO#1POC2CCl\ as substrates ð72JGU194\
74JGU15Ł[ The reactions were performed with two equivalents of amine in dry ether at temperatures
below −4>C\ and it appears that ynamine intermediates may be involved[ The range of phos!
phorylated aldoketenimines prepared in this way is shown in Table 6[
Cl RNH2, Et2O Cl
Cl RT Cl
Cl Cl Cl NHR
(181)
Cl Cl
Cl
NR Cl Cl
Cl • Cl Cl
Cl • •
N N
(182) (183)
Scheme 57
Ð*ÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐ
Entry Ketenimine Yield
")#
ÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐ
*
0 "RO#1POCH1C1NBut "RMe\ Et\ Prn# 75Ð099
1 "R1N#1POCH1C1NBut "RMe\ Et# 82Ð099
2 "MeO#"Et1N#POCH1C1NBut 72
3 "MeO#1POCH1C1N"0!adamantyl# 84
4 "MeO#1POCH1C1N!TMS 18a
ÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐ
*
a
"Me2Si#1NNa was used as the base[
R1 R2 R2 H
Ph3P=CR1R2 +
N • O PhP R1 = H
N
Ph NPh Ph3P Ph
R1R2 = H, Me
–O O
(184) (185)
Scheme 58
nonstabilized ylides "e[g[\ entry 7#\ a _nding attributed to the relative di.culty of inducing the
elimination of triphenylphosphine oxide from the betaine intermediates formed in the latter cases[
In general\ however\ yields of ketenimines were in the range 24Ð89)[ Other workers subsequently
extended the reaction to the synthesis of ~uorenylideneketenimines "entries 09 and 08# ð79BCJ1471\
78JCS"P0#1039Ł\ N!acyl ketenimines "entries 00 and 07# ð70CB0865\ 74LA1294Ł\ and vinyl ketenimines
"entries 01Ð04# ð71LA79Ł[ In many of these cases\ spectroscopic characterization alone con_rmed
the formation of the 0!azaallene system^ the ketenimines either underwent other reactions\ or were
deliberately converted into other products[ Fleeting ketenimines such as "075# and "076# could
not even be detected spectroscopically\ but underwent immediate cyclization to give a variety of
heterocyclic products ð78JCS"P0#1039Ł[ Finally\ because higher ketenimines "extended 0!aza!
cumulenes# are rare in the literature\ it is signi_cant that one of the earliest applications of the
isocyanate:ylide reaction involved the presumed intermediacy of Ph1C1C1C1C1NMe during
the reaction of Ph1C1C1C1PPh2 with methyl isocyanate ð58JA5001Ł[
Table 7 Ketenimines\ R0R1C1C1NR2\ prepared by the reaction of ylides\ R0R1C1PPh2\ with isocyanates\
O1C1NR2[
Ð*ÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐ
Entry Ketenimine Conditions Yield Ref[
")#
ÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐ
*
0 MeO1C"Ph#C1C1NBut 092>C 81 69JOC751
1 Ph1C1C1NC"CF2#2 Et1O\ RT 61 62DOK"101#517
2 MeO1C"Me#C1C1NAr "ArPh\ p!Tol\ 0!naphthyl# C5H5\ RT 79Ð84 63ACS"B#475
3 MeO1C"Me#C1C1NR "REt\ But# C5H5\ re~ux 89 63ACS"B#475
4 PhCO"Me#C1C1NR "RPh\ Et# C5H5\ RT 89 63ACS"B#475
5 Ph1C1C1NEt C5H5\ 099>C 74 63ACS"B#475
"autoclave#
6 Ph1C1C1NR "RPh\ 0!naphthyl\ c!C5H00# C5H5\ re~ux 79Ð89 63ACS"B#475
7 Me1C1C1NAr "ArPh\ 0!naphthyl# Mesitylene\ 039>C 24Ð39 63ACS"B#475
8 EtO1C"CN#C1C1NPh C5H5\ re~ux 9 63ACS"B#475
09 "1\1?!C5H30C5H3#C1C1NR "RPh\ p!Tol\ C5H5\ re~ux 46Ð87 79BCJ1471
p!C5H3Cl\ 0!naphthyl\ c!C5H00#
00 EtO1C"Me#C1C1NCOR "RPh\ OEt# C5H5\ RT a 70CB0865
01 PhCH1CH"Me#C1C1NPrn C5H5\ RT 84 71LA79
02 PhCH1CH"Me#C1C1NAr "ArPh\ p!Tol# C5H5\ RT a 71LA79
03 PhCH1CH"Ph#C1C1NPh C5H5\ RT a 71LA79
04 PhCH1CHCH1C1NPrn C5H5\ RT a 71LA79
05 BunCO"R#C1C1NPh "RBun\ n!C4H00\ n!C5H02# C5H5\ RT a 72CB1697
06 EtO1C"Me#C1C1NR "RPh\ C"1N!xylyl#But# Toluene\ RT a 74LA1294
07 EtO1C"Me#C1C1NCSPh Toluene\ 09>C a 74LA1294
08 "1\1?!C5H30C5H3#C1C1NCH1CHPh C5H5\ re~ux 77 78JCS"P0#1039
ÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐ
*
a
Yield not given[
N
Bn
• NPh
Ph • NPh
Ph
(186) (187)
Several variations on the basic procedure\ described above\ exist[ Phosphorus ylides other than
triphenylphosphoranes remain unexplored apart from the halophosphoranes "077#\ which reacted
Ketenimines 482
with phenyl isocyanate to a}ord C!phosphinoyl ketenimines "078# in 34) yield "Equation "22##
ð79TL2872Ł[ The HornerÐWittig reaction between anions derived from dialkyl alkylphosphonates
and phenyl isocyanate represents another successful route to ketenimines\ and some examples are
shown in Table 8 ð70JCS"P0#1616\ 75JHC486Ł[
PhN=C=O, petroleum O
But R
ether, –20 °C (But)2P
But P (33)
• NPh
X 45%
R
(188) (189)
X = Cl, Br; R = Me, Prn
Phosphorus ylides undergo successful reaction with cumulenes other than isocyanates[ Capuano
and Djokar prepared a number of N!imidoyl ketenimines\ EtO1C"Me#C1C1NC"1NAr#Ar\ from
stabilized ylides and N!imidoyl isothiocyanates ð74LA1294Ł[ Unfortunately\ ylides were not speci_ed[
Diphenylcarbodiimide has also been reported to react with alkylidenetriphenylphosphoranes
ð69JOC1965Ł^ however\ only IR spectroscopic evidence was obtained for the otherwise well!known
product Ph1C1C1NPh[ It appears that ylides containing an a hydrogen also react with diphenyl!
carbodiimide to produce labile ketenimines\ RCH1C1NPh "RPh\ EtO1C#\ that undergo further
reaction with another equivalent of ylide ð69JOC1965Ł[
F 3C F3C
F3C H2, 3.4 bar, PtO2 F3C
• NR EtOH • NR
CF3 CF3
F3C F3C
(190) R Yield of (190)(%)
c-C6H11 29
Ph 33
But 35
X Yield (%)
NO2 80 (100:0)
Cl 73 (81:19)
H 94 (70:30)
Me 84 (72:28)
OMe 94 (71:29)
Scheme 59
C6H6, 0-5 °C
MeO2C CO2Me + CN Br
9%
MeO2C CO2Me
MeO2C CO2Me
• • CN-Ar
Br N N Br ArN NAr
HO NHAr
(194) (195)
Scheme 60
NBut
•
MeO2C CO2Me MeO2C
CO2Me
ButNC, C6H6, RT
(34)
X X
X Yield (%) (199)
– 62
CH2 82
CMe2 63
CH2CH2 53
Ketenimines 484
CO2Me
ButNC, Et2O CO2Me
–20 °C :
MeO2C
MeO2C CO2Me CO2Me +
12% • CO2Me
MeO2C ButN
•
NBut
(197) (198)
CO2Me
MeO2C
MeO2C CO2Me
MeO2C
CO2Me
• •
ButN NBut
(196)
Scheme 61
CN
But But +
i, HCN, HF, CH2Cl2 But N
CN
ii, MeSO3H, crystallize 60%
iii, KOH
(201) (202)
But
NC
But • N
N
H
(200)
Scheme 62
O Ph O
Ph ButNC, CCl4 Ph O Ph N
X + X
Ph N
N X •
–
Ph NBut
(203) (204)
X Yield (%)
OEt 92
NEt2 66
Scheme 63
The oddest ketenimine synthesis of all "Equation "24## involves combination of t!butyl isocyanide
and ~uorenylideneborane "194# in a 2 ] 0 ratio to give the 0\1!azaborolidine!ketenimine "195# in 40)
yield ð82CB0440Ł[ The structure of "195# has been con_rmed by x!ray crystallography[
485 Ketenimines and P\ As\ Sb\ and Bi Analo`ues
NBut
3ButNC
toluene, RT N
N B (35)
B 51% N
• But
ButN
(205) (206)
S
[(Pri)2N]2P [(Pri)2N]2P
:
CNBut S8
[(Pri)2N]2P TMS • NBut • NBut
90%
(207) TMS TMS
(208)
Scheme 64
In 0857 Aumann and Fischer reported that the chromium carbene complex "104# reacted with
cyclohexyl isocyanide to give an air!sensitive compound ð57CB843Ł\ the structure of which was later
shown to be the h0!ketenimine complex "105# by x!ray crystallography ð75CB2030Ł[ With a twofold
excess of isocyanide\ the ketenimine ligand "106# could be displaced from the intermediate complex
and isolated in 67) yield "Scheme 54# ð67CB0112Ł[ Other nucleophiles such as pyridine also liberated
the ketenimine ð74CB841Ł[ The voluminous subsequent publications by Aumann and co!workers
contained examples of the N!bonded ketenimine complexes "R0XC1C1NR1#MLn\ in which X is
OR\ SR\ SeR\ NR1\ or N1CR1\ and MLn is Cr"CO#4\ Mo"CO#4\ W"CO#4\ Mn"C4H3Me#"CO#1\ or
Fe"CO#3 ð77AG"E#0345\ 82CB0756Ł[ However\ only in a few instances was the ketenimine then liberated
from the metal template on which it was constructed "e[g[\ from a tungsten complex with acetonitrile
ð76CB0828Ł\ and from a manganese complex with excess isocyanide ð77CB0974Ł#[ Two especially
interesting examples*a C!amino ketenimine "107# generated from an "aminocarbene#chromium
complex ð78CB0028Ł\ and a C!phenylthio!C!vinyl ketenimine "108# generated from an alkenyl!
"thiocarbene#chromium complex ð89CB1942Ł*are shown in Scheme 55[
c-C6H11NC c-C6H11NC
MeO MeO c-C6H11 –(CO)5CrCN(c-C6H11) MeO
C6H14, 0°C
Cr(CO)5 • N • N(c-C6H11)
78%
Cr(CO)5
(215) (216) (217)
Scheme 65
i, PhCOCl, NEt3
PhCO2 PhCO2
H 2N CN-R
ii, CN-R N R N
Cr(CO)5
Ph • N R = But (92%), Ph • NR
Ph
Ph Cr(CO)5 c-C6H11 (95%) Ph
(218)
PhS PhS
Cr(CO)5 2 CN-R, Et2O • N(c-C6H11)
84%
Ph Ph
(219)
Scheme 66
Insertion of isocyanides into vinylidene and allenylidene complexes of transition metals should
in principle open up routes to higher 0!azacumulenes analogous to those described above[ In fact\
the only higher 0!azacumulene complexes described to date appear to be the unstable\ readily
hydrolyzed manganese complexes "119# and "110#\ prepared as shown in Equations "26# and "27#
ð78JOM"268#292Ł[ The free ligands have not been detached from the metal[ Transient vinylideneÐ
titanium complexes "111#\ trapped by alkynes as the titanacyclobutenes "112#\ are implicated in the
synthesis shown in Scheme 56 ð81CC24Ł[ In this case the metallacycles reacted with isocyanides to
give isolable "and previously undocumented# C!allenyl ketenimines "113# in yields of 79Ð86)[
Other h3!complexed vinyl ketenimines "e[g[\ "114#\ "115#\ and "116##\ made by treating a variety of
organometallic precursors with isocyanides\ have been characterized crystallographically but not
dissociated from the metal template ð79JOM"089#C28\ 89CC296\ 82JA8735Ł[
Ph Ph
CN-R, Et2O, 20 °C
• Mn(CO)2Cp • • NR Mn(CO)2Cp (37)
R= But, c-C6H11, Bn (220)
487 Ketenimines and P\ As\ Sb\ and Bi Analo`ues
Ph Ph
CN-But, Et2O, 20 °C
• • Mn(CO)2Cp • • • NButMn(CO)2Cp (38)
Ph Ph (221)
R2 R3
3 steps R1 HMPA, RT
R1 • TiCp2
(222)
CN-But R1 NBut
R1 n-C6H14, RT
TiCp2 • •
80–97%
R2 R3 R2 R3
(223) (224)
R1 = Prn, n-C5H11, Ph
R2 = H, Prn, n-C5H11, Ph
R3 = Prn, Ph, TMS
Scheme 67
The insertion of isocyanides into h1!acyl organometallic complexes\ which are also close relatives
of Fischer carbene complexes\ di}ers from the processes described above in that the metal remains
attached to oxygen in the product[ The acylthorium complex "117#\ for instance\ reacted quan!
titatively with one equivalent of isocyanide to yield gummy ketenimines "118#\ which reacted in turn
with a second equivalent of reagent to yield complexes "129# as tractable solids "Scheme 57# ð75JA45Ł[
An analogous zirconium!complexed ketenimine "120# has been detected by NMR spectroscopy\
though it rapidly decomposed when the synthesis "Equation "28## was tried on a preparative scale
ð76JA1938Ł[
Cp Cp
O Cp O
CN-R, RT Cp Th But CN-R, RT Th But
(Cp)2Th(Cl)(η2-COCH2But) Cl
~100 % Cl • ~100 % •
CN-R
NR NR
(228) (229) (230)
R = Ph, But, 2,6-C6H3Me2
Scheme 68
Cl
Cp2Zr
Cl O
Cp2Zr CD2Cl2, RT
+ TMS (39)
CN
O ~100% •
TMS N
(231)
Ketenimines 488
The synthesis of ketenimines from isocyanides and carbenes has been approached from a di}erent
perspective by Werner and co!workers\ who treated isocyanide complexes of cobalt with diaryl
diazoalkanes as an external carbene source "Scheme 58# ð89AG"E#164\ 80CB174Ł[ Intermediate ket!
enimine complexes were found to have either the h1!C\C or h1!N\C structures "121# or "122# depending
on the substituents on carbon[ These complexes could not be disrupted with additional isocyanide\
but on treatment with iodine\ ketenimines "123# and "124# were liberated in yields of 37Ð69)[
Me
Ar2CN2 Ar Ar
Me2CO, –78 °C to RT N I2, Et2O, RT
CpCo(CNMe)(PMe3) Ar • NMe
54–67% Co 50–70% Ar
Cp PMe3
Ar = Ph, p-Tol, p-C6H4Cl (232) (234)
Me3P
NR
CpCo(CNR)(PMe3) Co NR
Cp •
Me2CO, –78 °C to RT I2, Et2O, RT
+
52–68% R = Me (48%)
N2 R = Me, c-C6H11 CH(Me)Ph (68%)
CH(Me)Ph
(233) (235)
Scheme 69
R1 R2 Yield (%)
Ph H 82
Prn H 62
Me Me 27
i, ButNC
Cl
PdCl2 ii, dbu
Pd • NBut (41)
)2 55%
MeO i, ButNC
MeOH, Na2CO3 ii, dbu MeO
(43)
Pd Pd 38%
•
Cl Cl Cl )2 NBut
Pd(OAc)2 (cat.)
R1 Cl
– + dbu, THF R1
+ C N R (44)
• NR2
R1 R2 Yield (%)
Ph But 65
Ph X 57
p-Tol X 40 X=
H2C=CH But 20
PhCH=CH But 20
CN-R3
R1 THF, reflux; or R1 • NR3
• C6H5Me, RT
PPh3 (45)
R2 Pt R2 PPh3
Ph3P Pt
X Ph3P
X
(237) (238)
R1 R2 R3 X Yield (%)
Me Me But Br 89
Me Me But Cl 78
-(CH2)5- But Br 79
Me Et But Br 79
Me Me 2,6-Xylyl Br 59
+
PhC≡N-O– Ph N
C6H6
PPh3 O • NPh
EtO2C P 68% EtO2C
EtO2C Ph3
(240) (239) (241)
Ph N
+ C6H6, 8 °C
X N O– + O
PPh3 X = H (74%) X = H (20% + 80%)
P
Cl (85%) Ph3 Cl (8% + 92%)
N
• N X + X
(242)
Scheme 70
Haszeldine and co!workers have shown that oxazetidines "132#\ isolated from the reaction of
tri~uoronitrosomethane with bis"tri~uoromethyl#aminoallenes "133#\ give excellent yields of N!
tri~uoromethyl ketenimines "134# upon ~ow pyrolysis ð69CC345\ 62JCS"P0#0450Ł[ The overall process\
shown in Scheme 60\ is e}ectively a metathesis reaction[
Formal ð1¦1Ł cycloaddition has been invoked to explain the reaction of alkyl isocyanates
Ketenimines 590
R1 F3C
F 3C CF3 N CF
R2 3 R1
R1 N CF3 N O, ∆ 200–300 °C, –HCON(CF3)2
• NCF3
• R1 = R2 = H, 47% N O R1 = R2 = H, 100%
R2
R2 R1 = H, R2 = N(CF3)2, 89% F3C R1 = H, R2 = N(CF3)2, 98%
R1 = R2 = N(CF3)2, 32% R1 = R2 = N(CF3)2, >90%
(244) (243) (245)
Scheme 71
with 0!diethylaminopropyne "Scheme 61# ð61TL0028\ 66JOC3150Ł[ Electrocyclic ring opening of the
iminooxete intermediate "135# leads to the formation of isolable C!carbamoyl ketenimines "136# in
moderate to good yields[
O=•=NR, RT NR NR
C6H6 or CCl4 O O •
Et2N
Et2N Et2N
(246) (247)
R Yield of (247) (%)
Me 78
Et 67
Bun 51
c-C6H11 45
2,6-C6H3Me2 35
Scheme 72
R1 X R1
+
• NR3R4 X– (46)
R2 NR3R4 R2
X = Cl, OSO2CF3
Cl Me
AgBF4, CH2Cl2, –60 °C +
• N BF4– (47)
NMe2 Me
591 Ketenimines and P\ As\ Sb\ and Bi Analo`ues
Cl
H O
i, cyclopentene, ZnCl2, CH2Cl2, 20 °C
ii, NaOH
N
70%, >97% ee
〈82JA2920〉 H
MeO
i, Tf2O, collidine, O
ClCH2CH2Cl, ∆
ii, H2O N
Scheme 73
+
Me2N Cl Et3N, MeCN +
ClO4– NMe2 ClO4– • • NMe2 ClO4–
+
Me2N Me2N
NMe2
(248)
Scheme 74
R2 R1 R2
El+ X– +
:
R1 N • N X– (48)
R3 El R3
The only truly isolable keteniminium salts bear bulky substituents that help to retard decompo!
sition[ Equation "38# shows an example in which N!methylation of a hindered ketenimine a}orded
a salt that survived recrystallization ð67JOC490Ł[ N!Methylation with trimethyloxonium tetra~uo!
roborate or hexachloroantimonate\ or with methyl ~uorosulfonate\ has subsequently been exploited
in the synthesis of a wider range of isolable keteniminium salts "138#Ð"140#\ one of which\ compound
"141#\ has even been examined by single!crystal x!ray di}raction ð71CB061Ł[
Bn Bn Bn
But But
+ + +
• N X– • N X– • N SbCl6–
R Me Me But Me
R = Pri, X– = FSO3–, SbCl6– X– = FSO3–, SbCl6–
R = But, X– = FSO3–, BF4–
(249) (250) (251)
But But
+
• N SbCl6–
But Me
(252)
toluene, ∆
3d 81%
i, AcCl
ii, NaN(TMS)2
Ph Ph
P 82% P
EtO EtO Ph
Ph OEt
(258) (257)
Scheme 76
Scheme 77
–
X Y
X • Y –Ph3P=Y
Ph3P • PPh3 X • • PPh3
Ph3P + PPh3
(261) (262)
Scheme 78
+
X • • PPh3 + 2 Ph3PMe Hal–
Scheme 79
i, MeI, CHCl3, 0 °C
C6H6, RT
S ii, NaOMe, MeOH, RT
H2C PPh3 + RN • S RHN
84–95% PPh3 67–75%
(265)
SMe NaN(TMS)2
C6H6, RT to 50 °C
RN RN • • PPh3
R = Me 71%
PPh3 (266)
Ph 86%
Prn 69%
Scheme 80
R
Ar* O
Li R Ar*
Ph
P • P (51)
–78 °C to RT
TMS Ph
(269)
Ar* = 2,4,6-C6H2(But)3 R Yield (%)
Ph 45
H 16
H Ph
:
:
• P But • P But
Ph H
But But
But But
(R)-(270) (S)-(270)
But
But But
But
TMS-O NaOH, THF, 70 °C
R (52)
P
But • P
R TMS But
R
R
(271)
R Yield (%)
Ph 90
2,4,6-C6H2Me3 52
P Ar*
R1, R2 = Me, 15%
R2 •
R1–R2 = (CH2)5, 48% R1
R1
i, BunLi, THF •
R2 *
H
ii, R1R2C=O
R1 P Ar
–78 °C to RT (274)
TMS P
:
• • P
Ar* 48–70%
R2 Ar*
(272) (273) Ar*
R1, R2 = aromatic R1 P R1
• •
31–62% R2 P R2
Ar*
(275)
Scheme 81
P\ As\ Sb\ and Bi Analo`ues 596
Markl and co!workers have also investigated variants of the Peterson ole_nation in which
chlorotrimethylsilane is eliminated[ For example\ the reaction between the lithiated tri!
methylsilylallenes "165# and the sterically crowded ArPCl1 yielded 0!phosphabutatrienes "166# by
sequential displacement of the chloride ion and elimination of TMS!Cl "Equation "42##
ð75AG"E#0992Ł[ Propargylic rearrangements must have occurred during the synthesis of 3\3!bis"tri!
methylsilyl#!0!phosphabutatriene "167# from 0\2!dilithiated bis"trimethylsilyl# allene "168# and
ArPCl1 "Equation "43## ð81TL0870Ł[ The monolithiated allene "179# and ArPCl1 initially produced
alkynes "170# as a mixture of geometrical isomers^ subsequent lithiation of "170# followed by addition
of electrophiles then gave 0!phosphacumulenes "171# "Scheme 71#[ This variant of the Peterson
ole_nation also works with the lithiated phosphaallene "172#\ from which the 0\3!diphos!
phabutatriene "173# was obtained as an "E#:"Z# mixture "67 ] 11# via the isolable 0!phosphaallene
"174# "Scheme 72# ð77AG"E#0259Ł[
Ar*PCl2
R1 Li R1
THF, –78 °C to RT
• • • P (53)
R2 TMS R2 Ar*
(276) (277)
R1 R2 Yield (%)
TMS TMS 10
Ph Ph 45
Me TMS 10(E), 1(Z)
Ar*PCl2
Li Li THF, –78 °C to RT
TMS
• • • P (54)
TMS TMS 26% TMS Ar*
(279) (278)
Ar*PCl2 P BunLi
TMS Li TMS
THF, –78 °C to RT Ar* TMS-Cl, or MeI
• • • P
TMS R Ar*
TMS
(280) (281) (282) R = TMS, Me
Scheme 82
Ar*PCl2 Cl 18-crown-6
Li
THF, –78 °C to RT Ar*P toluene, ∆ P • • P
• P *Ar
• P Ar*
TMS Ar*
TMS Ar*
(283) (285) (284) (E):(Z) = 78:22
Scheme 83
R1
• • PAr*
n
R2
(287)
Scheme 84
Me1C1C] has been shown to produce a 6 ] 2 mixture of the diphosphirane "180# and the 0!
phosphaallene "181# "Equation "46## ð80TL2576Ł[
Ar* Ph Ar*
CHCl3, KOBut, pentane, RT P ButLi, Et2O, –78 °C Ph
P • PAr* (55)
35% from (E), 47% from (Z) 62%
Ph Cl Cl
(288)
Ph
CHCl3, NaOH, BnNEt3+ Cl–
Ph Ar* hexane, RT Ar* BunLi, Et2O, –78 °C
Ph
• P Ph P • • PAr* (56)
35% 68% Ph
Ph
Cl Cl
(289)
Cl
Ar* Ar*
Ar* BunLi, Et2O, 0 °C P P
P P + • PAr* (57)
Ar*
H R = Ph, 37%, R
Ar*PHCl
R Li R P • PAr*
THF, –78 °C to 0 °C But, 35%,
Ar*
Me, 17%
(293)
Scheme 85
Treatment of the quadricyclane "187# with copper"II# chloride in deuteriated benzene gives
rise to the phosphaallene "188#\ characterized by NMR spectroscopy ð82BSF074Ł[ The postulated
mechanism "Scheme 76# assumes that corner metallation of a cyclopropane ring is followed by
cleavage of the C!00C!1 bond to form the intermediate "299#[ After a Grob!type fragmention of
the C!30C!6 bond and elimination of copper\ the resulting cyclopentadien!4!yl phosphaallene "290#
rearranges to the more stable 0!substituted isomer "188#[
P\ As\ Sb\ and Bi Analo`ues 598
Ar*PHCl
TMS-O THF, –78 °C to 0 °C
TMS-O H
R1 Li R1 P
R2 R1, R2 = H, alkyl, aryl R2 Ar*
(294)
+ 4
Cu Cu
(298) (300) (301) (299)
Scheme 87
But But
But
But
But Ph But
Ph • P Ph
But But
• P But Ph • • P
W(CO)5
Ph M Ph W(CO)5
M = Ni(CO)3, Cr(CO)5, (303) (304)
Mo(CO)5, W(CO)5
(302)
2[06[1[2 0!Arsacumulenes
By the end of 0882 there were only two documented syntheses of 0!arsacumulenes[ Bestmann and
Bansal prepared the ketenylidene l4!arsorane "294# by elimination of methanol from the stabilized
arsenic ylide "295# "Equation "47## ð70TL2728Ł according to the method previously described for the
corresponding phosphorus analogue ð64AG"E#523Ł "cf[ Section 2[06[1[0[0#[ Markl and Reithinger
have adapted one of the previously discussed Peterson ole_nation procedures "cf[ Section 2[06[1[1[0#
for preparing the unstable 0l2!arsabutatriene "296# as shown in Scheme 77 ð89TL5220Ł[ The product
dimerized spontaneously to the 0\2!diarsetane "297#[
509 Ketenimines and P\ As\ Sb\ and Bi Analo`ues
NaN(TMS)2
O toluene, RT
AsPh3 O • • AsPh3 (58)
MeO 60%
(306) (305)
(TMS)3C
i, THF, –78 °C
Ph Li (TMS)3C ii, NaOH, H2O–MeOH Ph As OMe
• + As OMe •
Ph TMS 52%
Cl Ph
C(TMS)3
Ph As Ph Ph
• • • • AsC(TMS)3
As 47%
Ph Ph Ph
C(TMS)3
(308) (307)
Scheme 88
Copyright # 1995, Elsevier Ltd. All R ights Reserved Comprehensive Organic Functional Group Transformations
3.18
Nitriles: General Methods and
Aliphatic Nitriles
MICHAEL NORTH
University of Wales, Bangor, UK
2[07[0 GENERAL METHODS FOR NITRILE SYNTHESIS 500
2[07[0[0 Synthesis via Substitution Reactions 501
2[07[0[0[0 Nucleophilic substitutions 501
2[07[0[0[1 Electrophilic substitutions 503
2[07[0[1 Synthesis via Addition Reactions 503
2[07[0[1[0 Addition to CC multiple bonds 503
2[07[0[1[1 Addition to CX multiple bonds 504
2[07[0[2 Synthesis via Elimination Reactions 506
2[07[0[2[0 Elimination from carbonyl derivatives 506
2[07[0[2[1 Elimination from carboxylic acid derivatives 506
2[07[0[2[2 Elimination from nitro compounds 519
2[07[0[2[3 Elimination from amines and amino acids 519
2[07[0[3 Synthesis from other Nitriles 519
2[07[0[4 Miscellaneous Methods of Synthesis 510
500
501 Nitriles] General and Aliphatic Nitriles
review of the more classical methods of nitrile synthesis[ The general methods used in the synthesis
of nitriles can be classi_ed as] by substitutions\ by additions\ by eliminations\ synthesis from other
nitriles and miscellaneous methods[ Each of these is discussed in turn[
NaCN AgCN
R CN R X R NC
Scheme 1
Where necessary\ a variety of methods are available for increasing the nucleophilicity of the
cyanide anion[ Thus\ use of hexamethylphosphoramide "HMPA# as the solvent\ and NaCN rather
than KCN\ results in coordination of the HMPA to the sodium ions\ and the formation of highly
nucleophilic naked cyanide ð67JOC0906Ł[ A similar e}ect can be obtained for KCN by using a
mixture of HMPA and 07!crown!5 ð67JOC0906Ł\ or just 07!crown!5 ð63JOC2305Ł[ For primary and
secondary alkyl chlorides which normally react with cyanide only very slowly\ use of DMSO as the
solvent and temperatures of 89Ð059>C result in improved yields ð59JOC146Ł\ as do glycolic solvents
such as diethylene glycol and polyethylene glycol!299 ð45ACS0086Ł[ Adsorption of NaCN or KCN
onto alumina also gives a highly reactive cyanide source ð68JOC1918\ 79SC168Ł[ The use of lithium
cyanide has been reported to give superior results due to its greater solubility in organic solvents\
such as acetonitrile and DMF ð53JOC0869Ł[
Although the displacement of halides by cyanide is often a straightforward reaction\ one problem
that is sometimes encountered is _nding a suitable solvent for both the organic halide and NaCN[
Alcohols are not always suitable solvents since alcoholysis of the halide can be a side reaction
ð37CRV078Ł\ and solvents such as HMPA and DMSO can cause puri_cation di.culties particularly
for large!scale reactions[ One solution to this problem is to use a two!phase organic:aqueous solvent
system\ and a phase!transfer catalyst such as a quaternary ammonium salt ð62JA2502Ł\ polysorbate!
79 ð78JOC3365Ł\ or 07!crown!5 ð64TL60Ł[ The crown ether catalyses both solid:liquid reactions "e[g[\
BnBr:dry KCN#\ and liquidÐliquid reactions carried out in an acetonitrile:water solvent system[ A
further possibility is to use sonication to induce a reaction between an alkyl halide dissolved in
toluene\ and solid KCN and alumina as described by Ando et al[ ð73CL614Ł[ The yield of nitrile
obtained in this way is reported to be higher than that obtained using 07!crown!5 as a phase transfer
catalyst[ An alternative approach is to use acetone cyanohydrin as the cyanide source\ since in the
presence of 0\4!diazabicyclo ð4[3[9Łundec!4!ene "dbu# or tetramethylguanidine this reagent converts
alkyl halides into nitriles ð82SC1212Ł[
Tertiary alkyl halides are not susceptible to substitution under standard SN1 conditions\ and
under SN0 conditions give the isonitrile[ One solution to this problem has been developed by Reetz
et al[ ð70AG"E#0906\ 72T850Ł[ Thus\ reaction of a tertiary alkyl halide with TMS!CN in the presence
of a catalytic amount of SnCl3 results in formation of the corresponding nitrile with retention of
stereochemistry as shown in Equation "1#[ The reaction is thought to proceed via the corresponding
isonitrile\ with the SnCl3 isomerising this functionality to the nitrile product[ Other groups which
are susceptible to SN0 type reactions such as a!chloro ethers also undergo this reaction "cf[ Section
2[07[1[3#[
TMS-CN/SnCl4
Cl CN (2)
TMS-Cl/NaCN/NaI
(3)
OH CN
O O
O
PPh2
PPh2
O
(1)
Cl N C NR2
H I2
Cp2Zr R2 NC
R1 + Cp2Zr R1 Cp2Zr R1 R1
Cl
Cl
R2 = But or TMS (2) (3)
O
CN
(4)
Scheme 2
Unlike unactivated alkenes\ cyanide adds with ease to both electron!de_cient conjugated alkenes
ðB!81MI 207!90Ł\ and electron!rich enol ethers and enamines[ However\ as these reactions inevitably
lead to nitriles containing heteroatoms\ they are dealt with in the appropriate sections later in this
chapter[
X X
TMS-CN/Eu(fod)3 CN
R R (4)
O OH
TMS!CN adds to a\b!unsaturated ketones in the presence of a variety of Lewis acid catalysts\ to
give either the cyanohydrin resulting from 0\1!addition\ or the 3!ketonitrile resulting from 0\3!
addition to the enone ð66OR"14#144\ 72T856Ł[ The product is determined by the structure of the
ketone\ although in some cases it is possible to isomerise the kinetically formed 0\1!adduct to the
thermodynamically more stable 0\3!adduct by prolonged reaction[ See also Section 2[07[1[3[2[
Acetone cyanohydrin can also be used as the cyanide source\ providing a catalyst is present[
Evans and Truesdale originally introduced the use of the cyanide ion as the catalyst at 019Ð039>C
ð62TL3818Ł\ though Lewis acid catalysts have since been found to be more e}ective[ Catalysts based
on lanthanide alkoxides ð82CL264Ł\ titanium and zirconium alkoxides\ and aluminum alkyls have
been used ð89CL0060Ł\ although with aluminum as the metal\ better results are obtained using
ligands which contain a phenol\ imine and an amide ð80CL034Ł[ Diethylaluminum cyanide is also
an e}ective cyanide source\ and has been reported to be advantageous in electronically di.cult
cases ð61JA3543Ł[
If cyanide is allowed to react with a carbonyl compound in the presence of a primary or secondary
amine\ then the product is the a!aminonitrile[ This procedure was discovered in 0749\ and is called
the Strecker reaction ð0749LA"64#16Ł[ Numerous reaction conditions have been developed for this
reaction\ allowing the preparation of a!aminonitriles derived from aromatic and aliphatic aldehydes\
aliphatic and monoaromatic ketones ð0779CB271\ 95CB0070\ 97CB1814\ 20JCS0280\ 20JCS0783\ 44OSC"2#164Ł[
A modi_ed procedure in which sodium hydrogensul_te is _rst added to the aldehyde to form the
bisul_te adduct has been reported to give higher yields in some cases ð62OSC"4#326\ 76TL436Ł[ The
mechanism of the Strecker reaction has been the topic of considerable debate[ However\ from a
synthetic point of view\ the most important point is that it is possible to treat a cyanohydrin with
an amine and obtain an a!aminonitrile[ This is often synthetically more convenient than the
traditional one!pot Strecker reaction ð23JA1086\ 23JPR164\ 33OSC"1#18Ł[ A chiral version of the Strecker
reaction has also been reported ð82BSF402Ł\ in which cyanide and ammonia are _rst reacted with a
chiral ketone to give a chiral aminonitrile[ This then functions as a chiral ammonia equivalent in a
second Strecker reaction with an aldehyde giving optically active aminonitriles after a hydrolytic
workup to cleave and regenerate the ketone!derived chiral auxiliary[ A number of other examples
of chiral Strecker reactions based on the use of chiral auxiliaries on the nitrogen atom have been
reported ð69CJC0770\ 60CB2483\ 79CB609\ 79LA101\ 74LA455Ł[
With hindered ketones\ the Strecker reaction sometimes gives the cyanohydrin rather than the
aminonitrile[ However\ it has been reported that sonication of the reaction mixture ensures for!
mation of the aminonitrile ð75TL2174Ł[ Alumina has been shown to be a good catalyst for the
Strecker synthesis of a!aminonitriles\ providing the reaction mixture is sonicated ð76CL576Ł[ The
method works well for aldehydes and acetophenone\ and has the advantage of a much simpler
workup procedure compared to more classical methods^ the solids are _ltered and the solvent
"acetonitrile# is evaporated to leave the aminonitrile[ Aminonitriles can also be prepared from the
TMS ethers of cyanohydrins by treatment with an amine ð73TL3472Ł[
Diethyl phosphorocyanidate can be used as a cyanide source for the Strecker reaction and this
has the advantage that the reaction can be carried out in an organic solvent under entirely anhydrous
conditions\ allowing the preparation of water!sensitive aminonitriles ð68TL3552Ł[ Mai and Patil
ð74SC046Ł have reported a general procedure for the preparation of a!aminonitriles from a wide
range of aldehydes\ methyl ketones and amines using TMS!CN as the cyanide source[ Thus\
treatment of the aldehyde or ketone with the amine for 0 minute at 099>C in the absence of a solvent
results in formation of the iminium salt which when treated with TMS!CN for a further minute at
099>C gives the a!aminonitrile[ The only limitation of this method appears to be that ammonia
cannot be used as the amine due to its volatility[
A reaction related to the Strecker synthesis is the addition of HCN to a preformed carbon
nitrogen double bond[ Suitable substrates for this reaction include imines ð23JA1984\ 35JA736Ł\ oximes
ð31JOC053\ 32JPR160\ 33JA0541Ł\ hydrazones ð0785CB51Ł and semicarbazones ð23JPR06\ 66JOC1990\
77OSC"5#223Ł[ The Lewis acid catalysed addition of TMS!CN to preformed imines and oximes has
also been reported ð64ABC460\ 64CL220Ł[ The most e}ective Lewis acid was found to be Znl1\ and by
General Methods 506
use of imines with a chiral auxiliary on the nitrogen atom\ chiral aminonitriles could be obtained
ð64CL626Ł[
With a\b!unsaturated aldehydes\ the Strecker reaction carried out under traditional conditions
often fails ð57JBC"132#5998\ 63ACS"B#206Ł[ However\ by using TMS!CN as the cyanide source\ and
reacting it with a preformed imine\ then good yields of b\g!unsaturated!a!aminonitriles can be
obtained ð73JOC1521Ł[
R R OH
(5) (6)
(7)
Scheme 3
Treatment of acid halides with the chlorophosphazine "7# "the reagent also contained 14) of the
eight!membered ring derivative#\ similarly gives nitriles in 4Ð84) yields ð62TL2714Ł[
Cl Cl
P
N N
Cl P P Cl
N
Cl Cl
(8)
A very large number of reagents have been reported to dehydrate unsubstituted amides to nitriles\
some of which are shown in Table 0[ For simple nitriles\ it is often su.cient to strongly heat the
amide and collect the nitrile by distillation as it forms ð44OSC"2#657Ł[ However\ many solids such as
silica\ pumice and alumina are known to catalyse the dehydration ð37CRV078Ł[ The Burgess reagent
"CH2O1CN−SO1N¦Et2# dehydrates even highly functionalised amides to nitriles in 71Ð81) yields
at RT in dichloromethane ð77TL1044Ł[ For small!scale reactions\ probably the reagent of choice is
tri~uoroacetic anhydride "TFAA# "either with pyridine ð66TL0702Ł or without ð89T7156Ł#\ which
dehydrates amides under very mild conditions at RT or below[ Furthermore\ the reagent causes no
racemisation of labile\ chiral centres ð89T7156Ł\ and gives only volatile by!products[ Chloro!
sulfonylisocyanate has also been reported to dehydrate chiral amides to nitriles without causing
racemisation ð71SC14Ł[ For large!scale dehydrations\ or for dehydrating unfunctionalised amides\
POCl2 ð96CB1698\ 23CB0651Ł or SOCl1 ð0782LA"163#201Ł is probably the reagent of choice[ In the case
of POCl2\ a number of di}erent reaction conditions involving addition of NaCl or P1O4 or use of
various solvents have been reported to result in increased yields ð37CRV078Ł[ Whilst both oxalyl
chloride and thionyl chloride act as dehydrating reagents in their own right\ addition of DMF to
the reaction mixture results in a much more reactive dehydrating agent[ It is thought that in both
cases the chloroiminium salt "8# is the actual dehydrating agent ð79SC368Ł[
Me + Cl
N Cl–
Me
(9)
N!Alkylated amides can also be converted into amides\ by a process called the Von Braun
reaction[ Thus\ N!t!butylamides are converted into nitriles upon treatment with POCl2 ð72OPP186Ł
or PCl4\ and N!TMS amides are converted into nitriles on treatment with an acid chloride ð61TL1946Ł[
Secondary amides are also converted into nitriles on treatment with Wilkinson|s reagent
"RhCl"PPh2#2# at 149>C ð69TL0852Ł[ Primary\ secondary and tertiary amides are all converted into
nitriles by treatment with bis"trimethylsilyl#amine at 079>C ð69JOC2142Ł[ Treatment of a primary
amide with two equivalents of TMS!Cl gives the N\O!bis!TMS adduct "09#\ which on treatment
with either a basic "Bu3NF# or acidic "FeCl2\ ZnCl1\ AlCl2\ or iron phthalocyanine# catalyst is
converted into the nitrile in 84Ð099) yield ð75TL236Ł[
N-TMS
R O-TMS
(10)
1\1?!Dipyridyl sul_te converts both amides and thioamides into nitriles ð75TL0814Ł\ as does CCl1
ð62TL1010Ł and PPh2:CCl3 ð60CB0929Ł\ whilst diethyl carbonate:N!methylmorpholine selectively
519 Nitriles] General and Aliphatic Nitriles
converts thioamides into nitriles ð74JOC1212Ł as does HgCl1:MeNH1 ð48JCS3939Ł[ Imino ethers are
converted into nitriles on treatment with sodium ethoxide ð57TL50Ł[
Aldehydes can be converted into the chain extended nitrile via the a\b!unsaturated nitro compound
as shown in Scheme 3[ Ketones are converted into the chain!extended nitriles on treatment with
tosylmethyl isocyanide "TsMIC# in the presence of potassium t!butoxide "Equation "5## ð62TL0246\
66JOC2003Ł\ or by treatment with carboethoxyhydrazine:HCN followed by Br1:NaOMe ð66JOC1990\
77OSC"5#223Ł[ The same chain!extending transformation can be carried out by treating either an
aldehyde or a ketone with 1\3\5!triisopropylphenylhydrazine followed by KCN in re~uxing methanol
ð66CC179Ł[ An alternative procedure involves treating a carbonyl compound with TMS!formamidine
"00# and sec!BuLi\ giving the enamine as shown in Scheme 4[ Exchange of the formamidine
for N\N!dimethylhydrazine followed by Ho}mann elimination with methyl iodide:base gives the
corresponding nitriles ð82TL4728Ł[ Electrochemical reduction of the nitro alkene in the presence of
TiCl3 gives the nitrile ð76S520Ł[
TiCl4/Et4N+TsO–
O +5– 6 e–
MeNO2
NO2
R 64–95% R CN
R
Scheme 4
511 Nitriles] General and Aliphatic Nitriles
R1 TosCH2N=C R1
O CN (6)
KOBut
R2 R2
R1
Me i, Me2NNH2
R1 TMS N ii, MeI R1
BusLi R2 N Me
O + CN
iii, NaOMe
R2 NBut R2
(11) NBut
Scheme 5
a!Amino ketones can be converted into imine derivatives\ as shown in Scheme 5\ which then
undergo a fragmentation reaction giving nitriles ð52HCA0089Ł[
O NX
R3 R3 R3 CN
N N
R1 R2 R1 R2
X = OH, O2CMe, O2CPh
Scheme 6
NC
R2 OR1 ddq/TMS-CN R2 OR1
(8)
LiClO4(cat.)
R3 R3
b\g!Unsaturated nitriles can be deprotonated with a suitable base such as LDA\ and the anions
then react with alkylating agents exclusively in the a!position\ providing a route to a!functionalised
b\g!unsaturated nitriles ð64TL3536Ł "see also Section 2[07[0[3#[ a\b!Unsaturated nitriles\ which are
readily prepared by a variety of routes "see Chapter 2[08#\ can also be deprotonated "LDA:HMPA#\
to give the same delocalised carbanion obtained from b\g!unsaturated nitriles\ and again alkylation
occurs a! to the nitrile ð64JOC0051\ 68JOC299Ł[ The readily prepared a!cyano allyl esters "01# undergo
a palladium!catalysed Carroll reaction\ leading to b\g!unsaturated nitriles as shown in Equation
"8# ð76JOC1877Ł[ Vinylboranes react with chloroacetonitrile in the presence of potassium 1\5!di!t!
butylphenoxide to give the corresponding b\g!unsaturated nitriles stereospeci_cally as shown in
Equation "09# ð70JOC118\ 75JOC287Ł[
O
Pd(PPh3)4, 100 °C
(9)
O
R CN R CN
(12)
R = H, or Bun
But
O–K+
R1 R1
But
+ ClCH2CN (10)
BR22 CN
g\d!Unsaturated nitriles can be prepared from allyl halides by reaction with cyanomethylcopper
as shown in Equation "00# ð61TL376Ł[ The reaction is highly speci_c for allyl halides\ as alkyl halides
and benzyl halides fail to react[ In a similar reaction\ allyl halides react with iodomethylzinc
iodide and either CuCN or an a!copper nitrile derivative to give g\d! and d\o!unsaturated nitriles\
respectively\ as indicated in Equation "01# ð78JA5363Ł[ The azo!Claisen rearrangement of allyl amides
is initiated by a variety of dehydrating agents such as TFAA\ triethylphosphite:iodine\ PCl4:Et2N
or COCl1:Et2N to give g\d!unsaturated nitriles as shown in Scheme 6 ð54JOC1453\ 82TL0342Ł[ In
addition to simple allyl amides\ a!aryl\ oxygen\ halide\ ester and nitrogen containing amides also
undergo this rearrangement\ giving a variety of functionalised g\d!unsaturated nitriles ð80TL068Ł[
The same rearrangement can be brought about starting from b\g!unsaturated azides by reaction
with PPh2 and a ketene "Scheme 7# ð80TL3930\ 82T4042Ł[
Br Br
+ CuCH2CN (11)
Br
CN
R3 R3
ICH2ZnI/CuX
X (12)
R2 Br R2
69–91%
R1 R1
X = CN, CH2CN, MeCHCN
513 Nitriles] General and Aliphatic Nitriles
O
R R • R CN
NH N
Scheme 7
R3
• O
R1 N3 PPh3 R1 N R4
PPh3
R2 R2
R1 N CN
• R3 R4
R2 R3
R4 R2 R1
Scheme 8
The ~uoride!initiated Michael addition of allyl silanes onto a\b!unsaturated nitriles provides a
route for the synthesis of d\o!unsaturated nitriles "Equation "02##[ The reaction is e}ective in both
inter! ð75JOC0634Ł\ and intramolecular senses ð75JOC0642Ł[ 0!Nitrocycloalkenes undergo a one!
pot reaction with trimethylsilylmethylmagnesium chloride followed by PCl2 to give terminally
unsaturated nitriles as shown in Equation "03# ð82CC558Ł[
CN CN
TMS F–
+ (13)
R R
NO2
( )n i, TMSCH2MgCl
( )n CN (14)
ii, PCl3
O Cl
COCl2 Et3N
N N
H
CN
•
N
•
Scheme 9
Aliphatic Nitrile 514
2[07[1[1[2 Aliphatic nitriles with aryl or heteroaryl substituents
The direct introduction of a cyanomethyl group onto an aromatic ring can be achieved by the
palladium!catalysed coupling of an aryl halide and cyanomethyltributyltin as illustrated in Equation
"04# ð73CL0400Ł[ The reaction works well with electron!rich aromatic systems\ but fails with electron!
de_cient species[ Alternatively\ in the presence of Cul and HMPA\ aryl halides react with the enolate
of alkyl cyanoacetates to give the a!arylmalonate derivatives\ which on heating with aqueous sodium
hydroxide decarboxylate give a!arylnitriles\ as shown in Scheme 09 ð72CL082Ł[ In the umpolun` of
this reaction\ arylzinc chlorides react with bromoacetonitrile in the presence of a Ni"AcAc#1 catalyst
and cyclohexyldiphenylphosphine to give a!arylnitriles in 26Ð81) yield ð76S39Ł[ Treatment of an
o! or p!hydroxy substituted benzyl alcohol with NaCN in DMF at 009>C results in substitution of
the alcohol by cyanide\ giving the benzylnitrile ð65JOC1491Ł[ The reaction is thought to proceed via
a methylenequinone intermediate as shown in Scheme 00[ Dimethyl!o! or p!"hydroxybenzyl#amines
can be displaced by KCN\ presumably by the same mechanism ð62T0820Ł[
CN
Br
Bu3SnCH2CN
PdCl2[P(o-tol)3]2
(15)
CO2Et CO2Et
CuI/HMPA NaOH
ArX + – Ar Ar
CN CN CN
Scheme 10
110 °C NaCN
HO O HO
OH CN
Scheme 11
As illustrated above\ there are a number of routes for the preparation of compounds of the type
ArCH1CN^ however\ more substituted a!arylnitriles are not so readily prepared by these methods[
Grigg et al[ have reported that treatment of an arylmethylenenitrile with an alcohol in the presence
of a ruthenium catalyst "RuH1"PPh2#3# results in coupling to give the arylmethinenitrile\ as shown
in Equation "05# ð70TL3096Ł[ Cainelli et al[ have shown that in the presence of KHFe"CO#3 and an
aldehyde\ phenyl acetonitrile undergoes a reductive alkylation giving a!alkyl!a!arylnitriles
ð64JCS"P0#0162Ł[ Arylmethylnitriles react with alcohols in the presence of sodium to give the a!aryl!
a!alkylnitriles ð55TL0498\ 56CPB0700\ 60JOC1837Ł[ Arylmethylenenitriles can be deprotonated with BuLi
"see also Section 2[07[0[3# to give a lithium anion that undergoes Michael addition to a\b!unsaturated
ketones\ providing access to a range of functionalised a!arylnitriles ð70T0816Ł[ Nitrile!stabilised
lithium anions add to arene chromiumtricarbonyl species giving a variety of a!arylnitriles after
oxidative elimination of the chromiun^ an example is shown in Equation "06# ð71JOM"139#C4\
82TL0288Ł[ The same anions also add to electron!de_cient nitrobenzene derivatives ð77LA192Ł[
R
RuH2(PPh3)4
ArCH2CN + ROH CN (16)
Ar
Ts Me i, Ts Me
N N
CN
Li
(17)
ii, I2
N N
(CO)3Cr Bn Bn
CN
515 Nitriles] General and Aliphatic Nitriles
Cyanide will add to aryl alkenes such as cyanostilbene\ giving 1\2!diphenylbutandinitrile
ð11JCS0588Ł[ Ni"PTol2#3 has been used to catalyse the Markovnikov addition of HCN to aryl alkenes
leading to a!arylacetonitrile derivatives ð74JOC4269Ł\ and a total synthesis of naproxen has been
achieved in this way as highlighted in Scheme 01[ The addition of HCN to styrene derivatives is not
so facile\ but use of ZnCl1 as a cocatalyst increases the yield in these cases "see also Section
2[07[0[1[0#[
CN CO2H
HCN/Ni(PTol3)4
Treatment of an aryl halide and a nitrile with sodium and liquid ammonia results in formation
of the a!arylnitrile via addition of the nitrile anion to a benzyne intermediate ð72JOC3286\ 74JOC0223\
76JOC0222\ 76JOC1508Ł[ The reaction is also e}ective in an intramolecular sense ð51JOC2725\ 62OSC"4#152\
70JOC3599Ł\ giving cyclic!a!arylnitriles with a 3Ð6 membered ring fused to the aromatic ring[ Nitrile
enolates also react with aryl and heteroaryl halides in a photochemical reaction\ giving a!arylnitriles
ð65JOC2260Ł[
Treatment of methylthioacetonitrile "see Section 2[07[1[4# with N!chlorosuccinimide "NCS# results
in formation of the a!chloro derivative[ FriedelÐCrafts reaction with an aromatic compound gives
the a!aryl!a!thiomethylacetonitrile which on reductive desulfurisation gives the arylacetonitrile\ as
shown in Scheme 02 ð71CPB2463Ł[ Deprotonation of a!cyanomethylphosphonate "see Section
2[07[1[7# with NaH:HMPA followed by addition of an aryl iodide and Cul results in formation of
the a!aryl!a!cyanophosphonate[ On thermolysis\ the phosphate group is eliminated and substituted
by an alkyl group from the phosphate ester\ as shown in Scheme 03 ð74CL0668Ł[
Cl ArH/SnCl4 Ar
NCS or TiCl4 Zn/AcOH
MeS CN MeS CN MeS CN Ar CN
Scheme 13
i, NaH/HMPA
RO CN RO CN CN
ii, ArI/CuI ∆
RO P RO P R
O O Ar Ar
Scheme 14
KCN CN
O (18)
CO2H
O
(13)
NH H2N CN
P2O5 PhMgBr HCN
CF3CONH2 CF3CN
Ph CF3 Ph CF3
Scheme 15
Active methylene compounds containing a nitrile group can be photolysed in the presence of
bromine to give a!bromonitriles ð89S657Ł and reaction of a cyanohydrin ether with NBS results in
formation of the corresponding a!bromocyanohydrin ether ð65JOC1735Ł[ The addition of cyanogen
chloride to an enol ether results in formation of b!chlorocyanohydrin ethers ð65JOC1735Ł\ and
a!iodomalononitriles undergo radical additions to alkenes\ leading to g!iododinitriles ð81JA3325Ł[
A number of methods are available for the preparation of optically active cyanohydrins\ based
on one of four basic methodologies] "i# use of a chiral catalyst "including enzymes# for the asymmetric
addition of HCN to aldehydes and ketones "this area has been reviewed ð82SL796Ł#^ "ii# resolution
of racemic cyanohydrins^ "iii# addition of HCN to optically active carbonyl derivatives^ and "iv#
addition of nucleophiles to chiral acyl cyanides[
The _rst catalyst to be discovered for the asymmetric addition of HCN to aldehydes was the
D!oxynitrilase enzyme isolated from almonds in 0897 by Rosenthaler ð97MI 207!90Ł[ This enzyme
"EC 3[0[1[09# which constitutes 9[3) by weight of almonds\ will catalyse the asymmetric addition
of HCN to a wide range of aromatic ð76AG"E#347\ 89S464\ 89T868\ 80JA5881\ 80SC0276\ 80TL1594\ 81TA0112\
82CB668Ł\ heteroaromatic ð76AG"E#347\ 89T868\ 80SC0276Ł and aliphatic aldehydes ð76AG"E#347\ 89S464\
89T868\ 80JA5881\ 80SC0276\ 80TL1594\ 81TA0112\ 82CB668Ł as well as methyl ketones ð89S464\ 80TL1594\
82CB668Ł[ The natural substrate for this enzyme is benzaldehyde ð54AG"E#0968Ł\ which is converted
into "R#!mandelonitrile in 87) yield with 88) ee[ In early synthetic work with this enzyme\ an
aqueous solvent was used\ and this is often the optimum condition[ However\ the enzyme can also
be immobilised onto cellulose ð76AG"E#347Ł\ used in organic solvents ð89S464\ 80TL1594\ 82CB668Ł\ or
crude almond meal can be used ð77TL3374\ 89T868\ 80SC0276Ł\ and in some cases these conditions give
superior enantiomeric excesses[ It is also possible to use acetone cyanohydrin as an in situ source of
HCN ð80JA5881\ 81TA0112Ł[
Oxynitrilase enzymes have been isolated from a variety of other sources\ but synthetic inves!
tigations have only been conducted on the enzyme derived from Sor`hum bicolour "EC 3[0[1[00#
ð89AG"E#275\ 89TL0138Ł\ and that derived from Hevea brasiliensis ð82TL3658Ł[ These enzymes have
complementary activity to the oxynitrilase derived from almonds\ as they always gives the
"S#!enantiomer of the cyanohydrin[ However\ the Sor`hum!derived enzyme has a much narrower
substrate speci_city than the almond!derived enzyme\ catalysing the addition of HCN only to
benzaldehyde derivatives ð89AG"E#275\ 89TL0138Ł[ Again\ the enzyme can be used in aqueous
ð89AG"E#275Ł or organic solvents ð89TL0138Ł\ and can be immobilised on Eupergit C ð89AG"E#275Ł[
The enzyme from Hevea brasiliensis has been reported to give "S#!cyanohydrins from both aromatic
and aliphatic aldehydes in transcyanation reactions with acetone cyanohydrin as the cyanide source
ð82TL3658Ł[
In 0868\ Inoue and co!workers reported that cyclic dipeptides "diketopiperazines# containing a
histidine residue catalysed the asymmetric addition of HCN to benzaldehyde giving optically active
mandelonitrile ð68MAC0978Ł[ The optimum catalysts were found to be cyclo!ð"S#!His!"S#!PheŁ "06#
ð70CC118\ 71MAC468Ł\ and cyclo!ð"S#!His!"S#!LeuŁ "07# ð78CL1008Ł\ which catalysed the formation of
"R#! and "S#! mandelonitrile respectively[ Catalyst "06# has been used to catalyse the asymmetric
addition of HCN to a large number of carbonyl compounds[ Aromatic ð75BCJ782\ 77AJC0586\
89JOC070Ł\ heteroaromatic ð77AJC0586\ 89JOC070Ł\ and aliphatic ð74MAC0644\ 77AJC0586\ 89JOC070Ł
aldehydes as well as ketones ð77AJC0586Ł were all found to be converted into optically active
cyanohydrins with ee|s of 4 to 86)[ Acetone cyanohydrin can be used as an in situ source of HCN
with catalyst "06#^ however\ this results in lower enantiomeric excesses in the cyanohydrins ð75CL820Ł[
The diketopiperazine "06# can also be incorporated into an insoluble polymer\ though this results
in a considerable decrease in asymmetric induction to a maximum of 07) ee ð83SC092Ł[ Although
the catalyst "07# has been studied less extensively than diketopiperazine "06#\ it has been observed
that not only does it give the opposite enantiomer of the cyanohydrin to the peptide "06#\ but that
it also gives the highest enantiomeric excesses with aliphatic aldehydes ð78CL1008Ł^ this is again in
contrast to "06# which reacts best with aromatic aldehydes[
A number of organometallic reagents based on chiral complexes of titanium\ aluminum\ tin and
magnesium have also been found to catalyse the asymmetric addition of HCN or TMS!CN to
aldehydes^ the various results are collected in Table 1[ Narasaka et al[ have described the use of the
titanium complex "08# in the asymmetric addition of TMS!CN to aldehydes ð76CL1962\ 77BCJ3268\
89CL0504Ł[ It was found to be necessary to use a full equivalent of the complex "08# in the presence
of 3Aý molecular sieves[ Oguni and co!workers have described a very similar catalytic system based
upon the modi_ed Sharpless catalyst ð89CC0253\ 81JCS"P0#2024Ł[ However\ in contrast to the complex
Aliphatic Nitrile 518
N N
O O
H H
N N Ph N N
H H
N N
H H
O O
(17) (18)
"08#\ only a catalytic amount of the Sharpless complex is required to catalyse the asymmetric
addition of TMS!CN to aldehydes[ The same research group ð80CC0641\ 82JOC0404Ł has reported
that the titanium complexes of chiral imino alcohols such as "19# also catalyse the asymmetric
addition of TMS!CN to aldehydes[ The tin"II# complex "10# of "¦#!cinchone was investigated by
Mukaiyama and co!workers ð80CL430Ł and found to catalyse the asymmetric addition of TMS!CN
to aldehydes[ Corey and Wang have reported that a mixed catalyst system based on the magnesium
complex of a chiral bisoxazoline catalyses the asymmetric addition of TMS!CN to aldehydes\ best
results being obtained with aliphatic aldehydes ð82TL3990Ł[
H
Ph
Ph
Ph O OH But N
CF3SO3SnO
/TiCl2(OPri)2
OH N OH
O
Ph
Ph
OH
N
(19) (20) (21)
The above methods all rely upon the use of TMS!CN as a cyanide source[ However\ Inoue and
co!workers ð80TL3222\ 81CL1332\ 81JA6858Ł have reported that the titanium complex of the peptide
derived ligand "11# "and related ligands derived from other amino acids# catalyses the asymmetric
addition of HCN to aldehydes giving the "R#!enantiomer of the cyanohydrin[ Based on molecular
modelling studies ð81JA6858Ł of the postulated catalytic intermediate\ the authors were able to design
a new ligand "12# derived from "S#!valine\ the titanium complex of which catalyses the formation
of "S#!cyanohydrins[ Interestingly\ although the titanium complexes of the ligands "11# do not
catalyse the asymmetric addition of TMS!CN to aldehydes\ the corresponding aluminum complexes
both of the peptides "11#\ and of the amino acid derivatives "13# do so\ but they do not catalyse the
asymmetric addition of HCN to aldehydes ð80SL452\ 81JOC5667Ł[ The aluminum complexes of a
variety of other N!protected amino acids and peptides were also found to catalyse the addition of
TMS!CN to aldehydes ð81JOC5667Ł[
Br
OH Ph
O OH
O
N
N CO2Me N
H Br N
H
(22) (23)
OH
O
N
N
H
R
(24) R = Pri
R = Bui
R = Ph
529 Nitriles] General and Aliphatic Nitriles
Table 1 Comparison of organometallic derivatives as catalysts for the asymmetric addition of cyanide to
aldehydes[
Ð*ÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐ
Aldehyde Catalyst Yield ee "con_`uration#
")#
ÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐ
*
Benzaldehyde "08# 68 85 "R#
Sharpless 73 80 "R#
"19# 56 74 "R#
"11# 77 77 "R#
Bisoxazoline:Mg 77 41 "S#
1!Methylbenzaldehyde "12# 85 81 "S#
2!Methoxybenzaldehyde "19# 65 45 "R#
"11# 60 74 "R#
"12# 68 86 "S#
2!Phenoxybenzaldehyde "19# 56 68 "R#
"11# 45 80 "S#
3!Methylbenzaldehyde Sharpless 68 54 "R#
"19# 57 60 "R#
3!Methoxybenzaldehyde Sharpless 77 66 "R#
"19# 51 80 "R#
3!Cyanobenzaldehyde "19# 59 19 "R#
1!Naphthaldehyde Sharpless 79 59 "R#
"19# 65 62 "R#
"11# 44 89 "R#
"12# 52 61 "R#
Furfural "11# 19 76 "S#
1!Thiophenecarboxaldehyde Sharpless 73 72 "R#
"19# 59 68 "R#
Butanal "19# 62 46 "R#
Heptanal "11# 60 55 "R#
Bisoxazoline:Mg 77 84 "S#
Nonanal "08# 74 82
"10# 78 61
Decanal "08# 72 74 "R#
"19# 37 55 "R#
Undec!09!enal "08# 81 82
Dodecanal "19# 37 55 "R#
1!Methylpropanal "19# 69 23 "R#
"10# 56 84
1\1!Dimethylpropanal "19# 47 69 "R#
"10# 38 72
Bisoxazoline:Mg 46 89 "S#
1!Ethylbutanal Bisoxazoline:Mg 75 80 "S#
1\1!Dimethylpent!3!enal "10# 16 82
Phenylethanal "08# 55 66
2!Phenylpropanal "08# 77 80
"19# 74 39 "R#
Cyclohexanecarbaldehyde "08# 66 57
"19# 61 54
"11# 74 43
"10# 68 85
Bisoxazoline:Mg 83 83 "S#
Sorbaldehyde Bisoxazoline:Mg 13 73 "S#
Propenal "19# 43 52 "R#
1!Methylpropenal "19# 51 74 "R#
"11# 89 61
E!But!1!enal "19# 69 78 "R#
E!1!Methylbut!1!enal "19# 57 85 "R#
"11# 11 26
2!Methylbut!1!enal "19# 52 78 "R#
"11# 63 69
Hex!1!enal "11# 82 74 "R#
Bisoxazoline:Mg 48 76 "S#
Hex!1\3!dienal "11# 67 59
E!1!Ethylhex!1!enal "11# 17 59
Hept!1!ynal "11# 67 59
Oct!1!enal "11# 72 78 "R#
Geranial Bisoxazoline:Mg 20 52 "S#
Cinnamaldehyde "19# 70 61 "R#
"11# 71 70 "R#
"12# 39 51 "S#
ÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐÐ
*
Aliphatic Nitrile 520
A number of enzymatic systems have been reported to resolve racemic cyanohydrins[ In particular\
lipases can be use to enantioselectively esterify\ transesterify\ or saponify cyanohydrins ð77TL5846\
78TL0806\ 80LA36Ł[ Usually\ the maximum yield from such a reaction would be 49)^ however\ it has
been reported that the lipase from Pseudomonas is compatible with the reaction conditions under
which quinidine\ anion!exchange resins\ or polymer!supported cinchona alkaloids reversibly catalyse
the transcyanation of aldehydes with acetone cyanohydrin ð81BCJ000\ 81JOC4532Ł[ Thus\ in the
presence of isoprenylacetate\ the enzyme catalyses the enantioselective esteri_cation of the
"S#!cyanohydrin\ which disturbs the equilibrium established in the transcyanation\ and eventually
results in high yields of "S#!cyanohydrin acetates "Scheme 05#[
R CN R CN
O quinidine
+
R acetone
cyanohydrin OH
R CN
Scheme 16
Johnson and co!workers have reported that the TiCl3!catalysed addition of TMS!CN to chiral
acetals followed by hydrolysis of the chiral auxiliary gives optically active cyanohydrins\ as illustrated
in Scheme 06 ð72JOC1183\ 73TL480Ł[ Condensations of esters with optically active sulfoxides give
b!ketosulfoxides "14# as shown in Scheme 07 ð81JOC6124Ł[ Addition of cyanide "from diethyl!
aluminum cyanide# to the carbonyl group of compounds "14# is controlled by the chirality of the
sulfoxide\ giving cyanohydrins with ×85) de[ Reetz et al[ have investigated the TiCl3!catalysed
addition of allyl silanes and silyl enolethers to a! and b!benzyloxyacyl nitriles "15# and "16#\
respectively ð74AG"E#878Ł[ In all cases\ a greater than 85) de was observed\ with the major isomer
being the product of chelation!controlled addition of the silyl derivative to the acyl cyanide[
O OH
TMS-CN/TiCl4 O
R
R
O R CN
CN OH
Scheme 17
O O O O OH O
LDA Et2AlCN NC
+ R2 S S S
R1 OEt Tol R1 Tol R1 Tol
R2 R2
(25)
Scheme 18
O O
BnO CN OBn CN
(26) (27)
Optically active benzylic and allylic cyanohydrins can be converted into the opposite enantiomer
under Mitsunobu conditions "triphenylphosphine\ dead\ 3!nitrophenylacetic acid#\ followed by
acidic hydrolysis of the resulting ester ð82T0952Ł[ However\ alkyl cyanohydrins are esteri_ed with
retention of con_guration under these conditions[ By contrast\ aliphatic cyanohydrins can be
inverted by treatment of a sulfonyloxy derivative with acetate followed by hydrolysis of the cyano!
hydrin acetate ð82CB668Ł[ Under these conditions\ aromatic cyanohydrins are partially racemised[
521 Nitriles] General and Aliphatic Nitriles
2[07[1[3[1 b!Oxygenated nitriles
For racemic b!hydroxynitrile synthesis based on lithium enolates of nitriles see Section 2[07[0[3[
Reactions between bromoacetonitrile and zinc result in formation of the corresponding zinc enolate\
which then reacts with aldehydes and ketones in the presence of TMS!Cl to give b!silyloxynitriles
ð89TL1194Ł[ Treatment of a nitrile with a boron tri~ate such as 8!BBN tri~ate results in formation
of the boron enolate of the nitrile which reacts with aldehydes leading to b!hydroxynitriles
ð71CL0390Ł[ A chiral b!hydroxynitrile synthesis has been reported ð81TA566Ł in which cyano!
methylzinc bromide adds to aldehydes in the presence of N!methyl!diphenylprolinol "DPMPM#
"17# giving b!hydroxynitriles in 63Ð82) ee[
Ph
N OH
Me Ph
(28)
But
N OH
OH
(29)
Alkenes can be converted into b!hydroxynitriles via a 0\2!dipolar cycloaddition with carbo!
ethoxyformonitrile oxide as shown in Scheme 08[ Saponi_cation followed by thermal decar!
boxylation!induced fragmentation of the intermediate isoxazoline results in the formation of
b!hydroxynitriles[ The reaction is stereoselective\ the stereochemistry of the b!hydroxynitrile being
determined by the geometry of the alkene ð72JOC255Ł[
b!Hydroxynitriles can be resolved via the enantioselective hydrolysis of the thioacetylesters using
lipase!P ð78CL0494Ł[ The presence of a sulfur atom in the cyanohydrin ester has been found to be
essential in order to obtain a good enantiomeric excess[ Attempts to use bakers| yeast for the
asymmetric reduction of 2!ketobutyronitrile\ has resulted in concomitant introduction of an ethyl
group\ giving the a!ethyl!b!hydroxynitrile\ as shown in Equation "19# ð78TL2700Ł[ However\
Aliphatic Nitrile 522
R1 –O R1 i, NaOH R1 OH
N+ O
ii, ∆
+ N
R2 CO2Et R2 R2 CN
CO2Et
Scheme 19
1!substituted!2!ketobutyronitriles are reduced by bakers| yeast\ giving a mixture of syn and anti
optically active b!hydroxynitriles in which the substituent in the 1!position determines the syn:anti
ratio ð78BCJ2740Ł[
O OH OH
Baker's yeast
CN CN + CN (20)
88%
Et Et
b!Ketonitriles can be prepared from ketones by forming the corresponding kinetic enolate with
LDA\ and then allowing the enolate to react with tosylcyanide ð70TL4900Ł[ Yields are between 45)
and 79) for cyclic ketones\ but linear methyl ketones give only low yields[ Ketone enolates also
react with cyanogen chloride to give b!ketonitriles ð69JOC050Ł[ This transformation can also be
achieved under nonbasic conditions by reacting a ketone with chlorosulfonylisocyanate ð62S571Ł[
In a related reaction\ enamines react with arylisocyanates ð54CB2551Ł or cyanogen chloride
ð48JA4399Ł to give b!ketonitriles after an acidic workup[ The dianion of a b!ketonitrile cannot be
prepared directly from the b!ketonitrile[ However\ the dianion can be generated by treatment of an
isoxazole with sodium methoxide as shown in Scheme 19 ð34JA0634Ł[ The dianion can then be
alkylated regiospeci_cally at the g!position to give substituted b!ketonitriles ð67TL3110Ł[ The dianion
of cyanoacetic acid can be prepared with butyllithium\ and reacts with acid chlorides to give
b!ketonitriles after a decarboxylative acidic workup ð72S297Ł[ Similarly\ TMS a!cyanocarboxylates
are deprotonated by LDA and react with mixed anhydrides to give b!ketonitriles as illustrated
in Equation "10# ð68TL0474Ł[ b\g!Epoxynitriles can be prepared from b\g!unsaturated nitriles by
epoxidation with mcpba ð64JOC0051Ł[
R1 O O
2LDA R2 – CN E+ E CN
R2 N –
or NaOMe
O R1 R2 R1
Scheme 20
i, LDA
R1 ii, R2CO2CO2Et
R1
iii, H3O+ R2
NC CO2-TMS NC (21)
O
Scheme 21
ArS OEt
(30)
Oxidation of a!thionitriles can give either the sulfoxide ð70S193\ 72BCJ146\ 73JA6789Ł or sulfone
ð76S341Ł\ depending upon the oxidising agent[ Optically active a!cyanosulfoxides can be prepared
either by the oxidation of the corresponding sul_de with a chiral oxaziridine ð81JA0317Ł or the
modi_ed Sharpless catalyst ð74NJC0Ł\ or by reaction of a nitrile enolate with a menthyl sul_nate
ð70JCS"P0#503Ł[ Nitrile enolates also react with sultines to give a!cyanosulfoxides\ and use of a chiral
sultine leads to the formation of optically active a!cyanosulfoxides ð70JOC4397Ł[ Optically active
a!cyanosulfoxides can also be prepared from suitable a!cyanovinylicsulfoxides by an intramolecular
ene reaction\ creating up to three new chiral centres with ×86) de as shown in Equation "11#
ð82T0720Ł[ a!Cyanosulfoxides undergo a stereospeci_c Pummerer rearrangement on treatment with
Aliphatic Nitrile 524
acetic anhydride\ giving a!thio!a!acetoxynitriles "Scheme 11# ð66TL0226\ 72BCJ146Ł[ Treatment of a
"b!arylethyl#cyanomethylsulfoxide with TFAA results in cyclisation of the Pummerer intermediate
as illustrated in Equation "12# ð77CPB0587Ł[ a!Cyanosulfoxides can be oxidised to the corresponding
a!cyanosulfones by treatment with mcpba^ the latter can then be deprotonated\ and react with 0\0!
dinitroalkanes to give b!nitro!a!cyanosulfones ð67TL652Ł\ and with alkyl halides to give a!alkylated!
a!cyanosulfones ð74BCJ654\ 74JOC1139Ł[ An alternative synthesis of ~uorinated a!cyanosulfones
involves deprotonating acetonitrile with LDA\ and reacting the resulting carbanion with a
per~uorosulfonyl ~uoride ð80S0194Ł[ The ~uorinated a!cyanosulfones can then be converted into
vinylcyanosulfones which undergo DielsÐAlder reactions to give cyclic a!cyanosulfones ð80S0194Ł[
Vinyl"aryl#sulfones can be converted into a!"arylsulfonyl#nitriles as shown in Scheme 12 ð67CPB673Ł[
Thus\ treatment with iodoazide followed by elimination of Hl gives the b!sulfonylvinylazide which
when heated eliminates nitrogen giving a!"arylsulfonyl#nitriles[ Cyanomethyl"aryl#sulfones can also
be prepared from arylsulfonyl chlorides and bromoacetonitrile by treatment with the compound
"20# ð89SC1180Ł[ Addition of methylsulfenyl chloride to acrylonitrile gives 2!chloro!1!methyl!
thiopropionitrile ð65JOC1735Ł[
O
S O
Tol
Et2AlCl S
CN Tol (22)
CN
mcpba O Ac2O S CN
RS– Na+ + Cl CN RS CN R
S CN
R OAc
Scheme 22
O
S CN
TFAA
(23)
S
R R
CN
I
IN3 N3 dabco N3 65 °C
ArSO2 ArSO2 ArSO2 ArSO2 CN
Scheme 23
O
EtO P Te–Na+
EtO
(31)
a!Cyanosulfoxides react with arenes in the presence of TiCl3 and TFAA to give a!aryl!a!cyano!
sulfoxides ð74TL366Ł[ Deprotonation of an a!cyanosulfone with NaH:Cul followed by addition of
an aryl iodide also gives a!aryl!a!cyanosulfones ð76CL776Ł[
The ylides of a!cyanosulfones act as sources of the corresponding carbenes which react with
alkenes to give cyclopropyl!a!cyanosulfones ð80CC369Ł[ The same reaction can be achieved starting
from a!chloro!a!thionitriles by treatment with SnCl3 followed by Et2N ð75JCS"P0#0652Ł[ Methyl
cyanodithioformate reacts as a dieneophile in the DielsÐAlder reaction\ giving cyclic\ a\a!dithio!
nitriles as shown in Equation "13# ð64JCS"P0#079\ 76JOC1331Ł[ Radicals generated from carboxylic
acids via a Barton decarboxylation undergo addition to acrylonitrile and its derivatives to give
a!pyridylthionitriles ð76T3186\ 81TL4906Ł[ The same chemistry can be used to prepare b!cyclic!a!
pyridylthionitriles by utilising v!tellurio!a\b!unsaturated nitriles as starting materials ð80TL3602Ł[
Chlorination of phenylthioacetonitrile with sulfuryl chloride gives a!chloro!a!phenylthioacetonitrile
525 Nitriles] General and Aliphatic Nitriles
which reacts with alcohols in the presence of silver ions to give a!oxygenated!a!phenyl!
thioacetonitriles ð80JA0933Ł[
R R
S S
+ SMe (24)
NC SMe
CN
R R
Scheme 24
MeS O MeS
MeS MeS CN
NH2
POCl3
(25)
pyridine
N N
H H
OMe OMe
b!Thionitriles can be prepared by the Michael addition of thiols onto b\g!unsaturated nitriles
ð36JA1217\ 44OSC"2#347\ 65JOC1735\ 67S591Ł[ Other sulfur!based nucleophiles such as benzenesul_nate
also add to b\g!unsaturated nitriles ð75TL4988Ł[ Cyanide undergoes Michael additions to vinyl!
sulfones\ also giving b!cyanosulfones ð37CRV078Ł[ Tosyl cyanide undergoes AIBN!initiated radical
additions to alkenes\ leading to b!cyanosulfones "Equation "15## ð76TL1742Ł[ With conjugated dienes\
0\3 addition occurs providing access to b\g!unsaturated d!cyanosulfones[ b\g!Unsaturated nitrile
g!silylenol ethers react with PhSCl to give b!phenylthio!g!ketonitriles as shown in Equation "16#
ð67SC120Ł[
Ts
TsCN/AIBN
(26)
CN
AIBN = 2,2-azobisisobutyronitrile
SPh
NC O-TMS PhSCl NC O
(27)
R R
EtO O
NCSe– NC Se
Cl CN NCSe CN CN
Scheme 25
Selenoacetals "23#\ react with TMS!CN in the presence of SnCl3 as a Lewis acid\ to give
a!cyanoselenides "24# as shown in Equation "17# ð82SL010Ł[ Only selenoacetals with simple alkyl and
aryl substituents have been investigated[ However\ seleno!ortho!esters "25# react similarly to give
a!cyanoselenoacetals "26# as shown in Equation "18#[ Treatment of the anion of malononitrile
derivatives with phenylselenyl bromide results in formation of a!phenylselenodinitriles which can
then undergo a radical addition to alkenes giving g!phenylselenodinitriles ð81JA3325Ł[ Reaction of a
malononitrile derivative with dialkylselenium dichlorides results in formation of the a!cyano!
selenium ylides ð61JOM"31#288Ł[ Electrolysis of an a!arylselenonitrile in the presence of Et2N and HF
results in the formation of a!~uoro!a!arylselenonitriles ð81TL2050Ł[
Phenylselenyl cyanide adds to unactivated alkenes in the presence of SnCl3 to give b!phenylselenyl
nitriles "27# ð71CC760Ł[ The reaction is a trans addition across the double bond as shown in Equation
"29# for the case of cyclohexene[ Phenylselenyl cyanide also adds stereo! and regiospeci_cally to
enamines giving b!seleno!a!aminonitriles ð71TL0250Ł without the need for a Lewis acid catalyst[
Similarly\ in the presence of BF2 phenylselenotoluenesulfonate adds to acrylonitrile giving 1!phenyl!
seleno!2!tosyl!propionitrile ð70JOC2138Ł[
CN
PhSeCN
(30)
SnCl4
SePh
(38)
N TMS-CN/PhCOCl N Ph
(31)
N N
H H
Tertiary amines are oxidised to iminium salts by chlorine dioxide[ Addition of NaCN then gives
a one!pot procedure for the conversion of amines into a!aminonitriles\ as shown in Equation "21#
ð77JA3718Ł[ Alternatively\ the amine can be oxidised to the nitrile oxide with hydrogen peroxide\
which on treatment with TFAA gives the iminium salt\ and addition of KCN gives the a!aminonitrile
ð79SC384\ 71H"08#1004Ł[ This transformation can also be achieved electrochemically[ Thus\ electrolysis
of a tertiary amine in methanol:water in the presence of NaCN gives the a!aminonitrile ð58JA3070\
66JOC1862Ł[ A related process for secondary amines involves chlorination to give the N!chloroamine\
followed by elimination to the imine and addition of HCN\ as shown in Scheme 15 for piperidine
ð68TL660Ł[ Cyclic a!methoxyamides and carbamates react with TMS!CN in the presence of
BF2 = Et1O or SnCl3 to give a!aminonitriles "Equation "22## ð70TL030\ 82T66Ł[ Thioamides react with
alkyl halides to give the S!alkylated salt which then reacts with KCN to form a!thio!a!aminonitriles
ð66JCS"P0#0700\ 76BSB"85#292Ł[ a!Hydroxylaminonitriles can be prepared by the oxidation of secondary
amines with hydrogen peroxide and sodium tungstate\ followed by the addition of cyanide to the
resulting nitrone ð76TL5358Ł[ Aminomalononitrile "H1NCH"CN#1# can be prepared from malono!
nitrile by formation of the oxime with sodium nitrite followed by reduction of the oxime to the
amine with aluminum ð62OSC"4#21Ł[
i, ClO2
R2 R1 ii, NaCN R2 R1
N N (32)
67-83% CN
R3 R3
HCN
N N N N CN
H H
Cl
Scheme 26
TMS-CN/TiCl4
MeO N CO2Bn NC N CO2Bn (33)
CO2Me CO2Me
The a!protons of an a!aminonitrile can be deprotonated by a suitable base\ provided the amino
group is suitably protected[ Reactions with electrophiles then provide a versatile route to a variety
of functionalised a!aminonitriles ð68S016\ 89CJC0294\ 89JCS"P0#2254\ 82SL488Ł[ b\g!Unsaturated!a!
aminonitriles react similarly ð76TL5068Ł[
Amines react with a\b!unsaturated nitriles via a Michael addition\ to give b!aminonitriles ð31CB020\
31JA0298\ 33JA614\ 34JA0960\ 34JOC166\ 44OSC"2#82\ 54JOC2578\ 70S264Ł[ In appropriate cases\ the amine
can react with more than one molecule of the a\b!unsaturated nitrile\ giving di! and trialkylated
amines[ This reaction has been recently reviewed ðB!81MI 207!90Ł[ Cyanide undergoes Michael
additions to nitroalkenes giving b!nitronitriles ð32CB0164\ 36JCS0499Ł\ and to a\b!unsaturated nitriles
leading to butanodinitrile derivatives ð0767LA"080#22Ł[ N!Tosylaziridines react with TMS!CN in the
presence of catalytic Yb"CN#2\ Y"CN#2\ or Ce"CN#2 ð89TL5268Ł\ or with acetone cyanohydrin in the
presence of lanthanoid"III# alkoxides ð82CL864Ł to give b!N!tosylaminonitriles in which cyanide
attacks the least hindered end of the aziridine[ When the boron enolate of a nitrile is formed with
Et1NBCl1\ followed by the addition of an aromatic aldehyde\ the product is not the expected
b!hydroxynitrile\ but the b!diethylaminonitrile "Equation "23## ð68SC442Ł[ v!Aminonitriles can be
prepared from cyclic a!aminoketones by Beckmann fragmentation of the derived imine or oxime
derivatives "see Scheme 5 for an acyclic example# ð52HCA0089\ 82SL479Ł[
NC Et2NBCl2 NC NEt2
(34)
ArCHO
R R Ar
Aliphatic Nitrile 528
2[07[1[7 Aliphatic Nitriles Bearing a P!\ As!\ Sb! or Bi!based Functional Group
a!Cyanophosphonates are valuable synthetic intermediates for the formation of a\b!unsaturated
nitriles via the WadsworthÐEmmons reaction "see Chapter 2[08#[ They can be prepared by the
Arbuzov reaction from an a!bromonitrile ð50JA0622\ 65JOC1735Ł\ or by reaction of a nitrile enolate
with diethyl chlorophosphate ð76S300Ł[ Displacement of the tosylate of a hydroxymethyl!
phosphonate by cyanide anion provides an alternative route to a!cyanophosphonates^ this is a
particularly useful way of introducing 02C! or 03C!labelled cyanide into these compounds
ð80JCS"P0#254Ł[ The alkene "28# undergoes Michael additions to give a!cyanophosphonates as shown
in Equation "24# ð89TL1794Ł[ a!Aryl!a!cyanophosphonates can be prepared from nitroalkenes and
silylphosphites by treatment with TiCl3 and zinc "Equation "25## ð76SC842Ł[ The enolate of an
a!cyanophosphonate can be formed\ and reacts with alkyl dihalides\ giving cyclic a!cyano!
phosphonates ð89PS"43#060Ł^ with Tf1NF to give a!~uoro!a!cyanophosphonates ð81JCS"P0#202Ł^ and
with phenylsulfenyl chloride leading to a!phenylthio!a!cyanophosphonates ð65JOC1735Ł[
O
P(OEt)2
CN
NH N
BOCHN + BOCHN (35)
NH NH CN
P(OEt)2
O O O
(39)
i, TiCl4 Ar CN
NO2 + (EtO)2PO-TMS (36)
Ar ii, Zn PO(OEt)2
NC OMe NC CO2Me
+ AsCl3 (37)
O-TMS AsCl2
TMS
Scheme 27
TMS
MeCN + TMS-OTf TMS CN (38)
TMS
Reaction of acrylonitrile with a TMS dialkylphosphite "or with a trialkylphosphite and TMS!Cl#
gives dialkyl 1!cyano!1!"TMS#ethanephosphonates ð71S804\ 72S806Ł[ Treatment of the lithium anion
of a nitrile with borane gives the lithium "a!cyanoalkyl#trihydroborate salt^ the lithium can then be
transmetallated to other alkali metals by treatment with the appropriate ~uoride salt ð78IC381Ł[
Scheme 28
Copyright # 1995, Elsevier Ltd. All R ights Reserved Comprehensive Organic Functional Group Transformations
3.19
a,b-Unsaturated and Aryl Nitriles
MILTON J. KIEFEL
Monash University, Vic., Australia
2[08[0 GENERAL METHODS 530
2[08[1 NITRILES BEARING AN a\b!VINYLIC BOND 532
2[08[1[0 a\b!Alkenic Nitriles without Further Unsaturation 532
2[08[1[1 a\b!Alkenic Nitriles with Further Unsaturation 535
2[08[1[2 a\b!Alkenic Nitriles with Halo!substituents 538
2[08[1[3 a\b!Alkenic Nitriles with Oxy`en!based Substituents 549
2[08[1[4 a\b!Alkenic Nitriles with Sulphur!based Substituents 543
2[08[1[5 a\b!Alkenic Nitriles with Se! and Te!based Substituents 545
2[08[1[6 a\b!Alkenic Nitriles with Nitro`en!based Substituents 545
2[08[1[7 a\b!Alkenic Nitriles with P!\ As!\ Sb! and Bi!based Substituents 548
2[08[1[8 a\b!Alkenic Nitriles with Si! and B!based Substituents 559
2[08[1[09 a\b!Alkenic Nitriles with Metal Substituents 550
2[08[2 NITRILES BEARING AN a\b!ARYL OR !HETARYL SUBSTITUENT 550
2[08[2[0 General Methods 550
2[08[2[1 Benzonitrile and Substituted Benzonitriles 553
2[08[2[2 Polycyclic Aromatic Nitriles 556
2[08[2[3 Heterocyclic Aromatic Nitriles 558
2[08[3 NITRILES BEARING AN a\b!TRIPLE BOND 563
530
531 a\b!Unsaturated and Aryl Nitriles
vinyl cuprates^ and "iv# by elimination\ such as in the dehydration of oximes[ Whilst speci_c examples
of these general approaches towards a\b!unsaturated nitriles will be presented throughout this
chapter\ it is appropriate at this stage to give an overview of these techniques[
The alkenations of aldehydes and ketones with cyanomethylenetriphenylphosphorane
ð50JCS0155Ł or diethyl cyanomethylenephosphonate ð62T1326Ł typically give the best results when
aromatic carbonyl compounds are employed ðB!72MI 208!90Ł\ although a few e.cient methods with
aliphatic carbonyl compounds have been reported ð60JOC1915\ 61TL558\ 63S758\ 66S518\ B!72MI 208!90Ł[
A modi_cation of this approach involves the use of cyanomethyldiphenylphosphine oxide in the
presence of base "Equation "0## ð66S015Ł[ In this way\ E!1!alkenenitriles are prepared with ×89)
selectivity for aromatic aldehydes and ½64) selectivity for aliphatic aldehydes and in excellent
chemical yield "generally ×89)#[ 0\1!Diketones can also react under Wittig conditions with cyano!
methylenetriphenylphosphorane to give the corresponding dialkene nitrile ð65T1868\ 66S455Ł[
O
ButOK
RCHO + P CN CN + (1)
Ph R R CN
THF or DMF
Ph trans cis
Vinyl halides generally have low reactivity towards nucleophilic displacement ð80COS"5#114Ł[ For
the preparation of vinyl nitriles\ the use of copper cyanide with base under high temperatures
"×199>C# is typically required ðB!69MI 208!90Ł[ However\ the use of potassium cyanide in the
presence of catalytic Pd"9# and 07!crown!5 "Equation "1## requires much milder conditions "59Ð
099>C# ð66TL3318Ł[ The reaction is highly stereospeci_c and high yielding "74Ð87)#[
R1 R3 R1 R3
Pd(PPh3)4, 18-crown-6
+ KCN (2)
Br benzene CN
R2 R2
a\b!Alkenic nitriles can also be prepared readily from a\b!alkynenitriles "see Section 2[08[3 for
the preparation of nitriles bearing an a\b!triple bond#[ Lithium aluminum hydride adds in a trans
manner to alkynenitriles to provide the alanate "0# "Scheme 0#\ which upon acidi_cation leads to
the E!a\b!unsaturated nitrile "1# ð68S329Ł[ Addition of an organocopper"I# reagent to an alkynenitrile
gives the a!cyanocuprate "2# "Scheme 1# which upon acidi_cation provides the 1!alkenenitrile "3#
ð67S343Ł[ It is worth noting that in this instance\ the R0 and CN groups "Scheme 1# are cis to each
other "cf[ Scheme 0#[ Furthermore\ addition of an organocuprate to an alkyne provides the vinyl
cuprate "4a# "Scheme 2# which\ upon exposure to cyanogen chloride in THF\ gives the corresponding
1!alkenic nitrile in ×89) yield ð66S673Ł[
CN CN
LiAlH4 H+
R CN CN
Al R
H2
R R
(1) (2)
Scheme 1
R1
R2[CuX]M H+
R1
R1 CN CN M
R2 CN
THF or Et2O R2
Cu X
(3) (4)
Scheme 2
R1 R1
[R2CuX]MgHal ClCN
R1 H MgHal
R2 R2
THF or Et2O THF
Cu X CN
(5a)
Scheme 3
Bearin` an a\b!Vinylic Bond 532
Elimination processes are also of interest as a general route into a\b!unsaturated nitriles[ The
dehydration of oximes\ an important method for the synthesis of saturated nitriles\ can also be
applied to the preparation of unsaturated nitriles[ In one reported example\ allylic nitro compounds
are deoxygenated with carbon disulphide under phase transfer conditions to provide the cor!
responding allylic oxime which is then dehydrated to an a\b!alkenic nitrile "Scheme 3# ð89SC854Ł[
Saturated nitriles can themselves be transformed into a\b!unsaturated nitriles via oxidative elim!
ination of an intermediate a!phenylselenonitrile with hydrogen peroxide "Scheme 4# ð63TL1168Ł[
Scheme 4
Li
N
i, SePh H2O2
CN CN
ii, PhSeSePh CN
Scheme 5
O
O CN
(EtO)2P CN
steps
NaH
RO RO
(5) (6)
O
(7)
Scheme 6
533 a\b!Unsaturated and Aryl Nitriles
Moderate yields of several simple alkyl a\b!unsaturated nitriles from carbonyl compounds have
also been achieved using either O!ethyl S!cyanomethyl dithiocarbonate "7# or S!cyanomethyl
diethyl phosphorothioate "8#\ also in a two!phase system employing catalytic methyl!
trioctylammonium chloride "Scheme 6#[ It is believed that the reaction proceeds via the thiirane "09#
which\ upon extrusion of sulphur\ produces the nitriles in 25Ð68) yield ð68S789Ł[ Generally higher
yields result from the use of the dithiocarbonate "7#[
S R1 O
+
EtO S CN R2 R3 S R2 R1
(8)
NaOH, H2O, MeCN R2 R1 –S
(C8H17)3N+Me Cl– R3 CN CN
O R1 O R3
+ (10)
(EtO)2P
S CN R2 R3
(9)
R1 = H, Me; R2 = H, alkyl; R3 = alkyl
Scheme 7
Cl CN CN
O (3)
( )n Bun3Sb ( )n
n = 1, 2
Cl
Bun3Sb H Cl
O Bun3Sb
CN OH
2
R1 R
(11) (12)
Acetonitrile can itself be used in the direct conversion of aliphatic ketones into a\b!alkenic nitriles
ð66S518Ł[ The use of potassium hydroxide pellets as base in acetonitrile solution overcomes many
of the problems usually associated with this type of reaction\ most notably the aldol condensation
of the ketone under the polar\ protic conditions normally required for this transformation[ The
reaction gives moderate to excellent yields "29Ð79)# of a\b!unsaturated nitriles^ lower yields result
from ketones which are easily enolized "e[g[\ acetophonone# ð66S518Ł[ Interestingly\ the reaction
between acetonitrile and cyclohexanone "Equation "3## provides the a\b!unsaturated nitrile con!
taminated with the b\g!unsaturated nitrile ð66S518Ł[ The latter component constituted about 19)
of the product\ and could be easily separated from the desired conjugated nitrile[ This result is
contrary to the reaction between cyclohexanone and cyanoacetic acid which provides only the
b\g!unsaturated product after decarboxylation of the intermediate cyanoacrylic acid ð40OS"40#14Ł[
O
MeCN, KOH CN CN
+ (4)
4.5 : 1
Scheme 8
Electrooxidative cleavage of the C0S bond in the ethylthiol "03# "Equation "4##\ using bromide
ion as the electrolyte\ results in the smooth formation "56Ð67) yield# of simple alkyl and branched
alkyl a\b!unsaturated nitriles ð75TL3066Ł[ As with the oxidative elimination of selenoxides\ this
oxidative elimination process results in essentially 0 ] 0 mixtures of cis]trans isomers[
Reductive eliminations can also lead to alkenic nitriles "Equation "5##[ Thus\ exposure of the
a!cyano!b!nitrosulphone "04# to sodium sulphide in DMF at room temperature provides the cor!
responding a\b!unsaturated nitriles in good yield ð67TL652Ł[ In this way several acyclic and cyclic
alkyl substituted a\b!alkenic nitriles have been prepared\ again as 0 ] 0 mixtures of geometrical
isomers[ The direct dehydrocyanation of 0\1!cyclobutenedicarbonitrile "05# with sodium hydroxide
at ×199>C results in moderate yields of 0!cyclobutanecarbonitrile ð62JOC364Ł[ The same product
can be obtained by the dehydrochlorination of 1!chlorocyclobutanecarbonitrile during exposure to
base under much milder conditions "009>C# ð62JOC364Ł\ although problems with the formation of
the requisite chloronitrile substrate ð51JOC311Ł make this approach impractical on a preparative
scale[
R1 R3 R1 R3
Na2S, DMF
R2 CN (6)
O2N SO2Ar R2 CN
(15)
CN
CN
(16)
The use of alkynes in the preparation of a\b!unsaturated nitriles has already been mentioned in
the introductory remarks[ Further to this\ hydroboration of alkynes with bis"0\1!dimethyl!
propyl#borane in THF gives the corresponding alkenyldialkylborane "06# "Scheme 8# which\ upon
exposure to copper"I# cyanide and copper"II# acetate in HMPA\ produced the desired E!1!alkenic
nitriles "07# in excellent yield ð80CC637Ł[ The presence of a small amount of water in the _nal step
of this transformation is essential for cyanoalkene formation ð63BCJ1400\ 78CC155Ł[
R22BH, THF CuCN, Cu(OAc)2, HMPT, H2O
R1 R1 R1
BR22 CN
(17) (18)
Scheme 9
CN
CN CN
O O
(20) (21) (22)
In the early 0889s it was found that the reactions of organozinc halides with p!toluenesulphonyl
cyanide provide an excellent entry into a\b!unsaturated nitriles ð82TL3512Ł[ This method is illustrated
in Equation "7#[
TsCN, THF, 0 °C to 25 °C
Cl ZnI Cl CN (8)
72%
O R1 R2 O
O Li R1 R2 O
R1 R2 O LDA R1 R2
TMS
(EtO)2P (EtO)2P
–78 °C (EtO)2P CN –78 °C
CN
CN
Li
(23) (24)
R1
R1
R2
R2 CN
(25)
LDA = lithium diisopropylamide
Scheme 10
O CHO
P(OEt)2 + CN (9)
CN
O
OH NC P(OEt)2 OR
CN
OH CHO OR
Many examples of the synthesis of a\b!alkenic nitriles with further unsaturation involve
compounds containing an aromatic ring\ often deriving from aromatic carbonyl compounds
ðB!72MI 208!90Ł[ In one such example\ involving cyanophosphates "29#\ the cyanophosphorylation
of aromatic ketones with diethyl phosphorocyanide in the presence of lithium cyanide a}ords "29#
"Scheme 00#[ Treatment of the cyanophosphates "29# with boron tri~uoride etherate then leads to
the a\b!unsaturated nitriles in good to excellent overall yield "50Ð83)# from the ketone ð73TL316Ł[
Interestingly\ the cyanophosphate "20#\ derived from an aliphatic ketone\ remains intact under the
dephosphorylation conditions[
O
O
O (EtO)2P CN
CN P(OEt)2
R1 O BF3•Et2O
R1
Ar NC Ar
LiCN R1
R2 Ar R2
R2
(30)
Scheme 11
O
P(OEt)2
O
CN
Ar
(31)
The reactions of aromatic carbonyl compounds with an organotellurium ylide also results in the
formation of 1!alkenic nitriles ð77JOC3751Ł[ Thus\ condensation of various para!substituted aromatic
ketones with the cyanodibutyl telluronium ylide "21# gives the corresponding aryl a\b!unsaturated
nitrile "22# in good yield "50Ð72)# and high E!selectivity "up to 013 ] 0 E ] Z#[
Bun CN
Te+ –CHCN
Bun R
(32) (33)
Organometallic chemistry when applied to aryl halides also furnishes a\b!unsaturated nitriles[ In
this case\ the Heck reaction involving the palladium!catalysed coupling of an aryl iodide with
acrylonitrile provides the corresponding aryl a\b!unsaturated nitrile in 76Ð83) yield "Equation
"09## ð78JOM"260#286Ł[ This process gives mixtures of E! and Z!isomers\ although slightly in favour
of the Z!geometry[
Pd(OAc)2, H2O, K2CO3, 80–100 °C
Ar I + Ar (10)
CN CN
537 a\b!Unsaturated and Aryl Nitriles
The interest in organic molecules as synthetic metals ð73NAT008Ł has led to the synthesis of
four thiophene!fused tetracyanoquinodimethanes "e[g[\ "23##[ These compounds were prepared in
04Ð26) yield by the titanium tetrachloride mediated condensation of the corresponding quinone
with malononitrile "19 equivalents# in chloroform containing pyridine "39 equivalents# ð75CC0668Ł[
NC CN
S S
NC CN
(34)
O CN
R NaOH (aq.) R
(11)
CN
S
(37)
CN
(38)
a\b!Unsaturated nitriles containing an additional triple bond can also be prepared from the
reaction of potassium cyanide with the quaternary salt of pyridazine 0!oxide "28#\ formed by the
reaction of pyridazine 0!oxide with either dimethyl sulphate or benzoyl chloride "Scheme 01#[ As
before\ only poor yields of the desired b!ethynylacrylonitriles "19Ð29)# were achieved ð62T1326Ł\
and as mixtures of geometrical isomers[ The reaction is believed to proceed via the dihydro derivative
"39# which undergoes electrocyclic opening to "30# which leads to the alkyne products upon elim!
ination of N1 and R20OH[ The intermediacy of the dihydro compound "39# is supported by its
slow conversion to the cyanopyridazine "31# "when R0 H# under the reaction conditions ð62T1326Ł[
R1 R2 Me2SO4 R1 R2 KCN R2
N N N N+
or PhCOCl R1 CN
O OR3
(39)
R1 = Ph, Me; R2 = H, Me
Scheme 12
Bearin` an a\b!Vinylic Bond 538
CN R1 CN
R1 N R2
R2 R CN
N N
N N N
OR3
OR3
(40) (41) (42)
The preparation of cyanoallenes "Equation "01## can be achieved by the treatment of substituted
1!propynols with potassium cyanide and HBr in the presence of copper cyanide and copper
ð57JCS"C#180\ 80COS"5#114Ł[ Alternatively\ the propynol can _rst be converted into the halide and then
treated with copper cyanide ð80COS"5#114Ł[
R R CN
CuCN, KCN, HBr, [Cu], 76 h
HO • (12)
R R
R = alkyl
Cl
Ph3P CN
CN
Cl R
R (13)
∆, 2–4 h Cl
O
Cl
An alternative method for the preparation of a!halo!a\b!alkenic nitriles involves the use of the
readily available arsonium salt "32#[ Treatment of the arsonium bromide "32# with iodine in pot!
assium carbonate a}ords the iodoarsonium iodide "33# which\ without isolation\ was reacted with
a variety of aldehydes "RAr\ alkyl# to give the corresponding a!iodo!a\b!unsaturated nitriles in
good to excellent yield "47) when Ralkyl^ 79Ð86) when RAr# "Scheme 02# ð78SC1528Ł[
+ + R I
Ph3As CN I2, K2CO3 Ph3As CN RCHO, K2CO3
Br– I– CN
I
(43) (44)
Scheme 13
The use of a novel intramolecular Wittig reaction has been developed for the synthesis of
b!per~uoroalkyl!a\b!alkenic nitriles ð80JCS"P0#376Ł[ It was found that per~uoroacylmethylene!
triphenylphosphoranes were highly stable and did not react with aldehydes under Wittig conditions[
To overcome this problem\ treatment of the per~uoroacylcyanomethylenetriphenylphosphorane
"34^ Rf CF2 or C2F6# with an aryl or alkynyl lithium reagent leads to the ylide anion "35# "Scheme
03#[ Acidi_cation of "35# results in a spontaneous intramolecular Wittig reaction to give the desired
~uorinated a\b!unsaturated nitrile in excellent yield "89Ð85)# ð80JCS"P0#376Ł[ The products from
549 a\b!Unsaturated and Aryl Nitriles
this transformation are predominantly the E!isomers\ and in no examples did the authors observe
nucleophilic attack at the cyano group in "34#[
CN CN
R CN
Ph3P RLi Ph3P H+
Rf R
–O
Rf
O Rf
(45) (46)
Rf = CF3, C3F7; R = aryl, alkynyl
Scheme 14
Scheme 15
Treatment of the `em!dicyanoepoxide "36^ RAr\ alkyl# with Li1NiBr3 leads to the bromo!
enolate "37# which can then be trapped with acetic anhydride providing various 1!acetoxy!2!bromo!
1!propene nitriles "Scheme 05# ð75TL4380Ł[ The yields for this transformation are excellent "68Ð
87)#\ and the product is predominantly the Z!isomer when Raryl "typical Z ] E ratio around
2 ] 0#\ although 0 ] 0 mixtures of geometrical isomers result when Ralkyl[
CN Br OLi Br OAc
R Li2NiBr4, THF Ac2O, pyridine
CN
O R CN R CN
(47) (48)
R = Ar, alkyl
Scheme 16
O
R1 CN
(EtO)2P CN
R2 OBut NC
OBut
H
ButO
(49) (50) (51)
The reaction of saturated aliphatic aldehydes with acrylonitrile in the presence of tri!butylphos!
phine "9[1 equivalent# and triethylaluminum "9[0 equivalent# at 79>C in dichloromethane under
pressure a}ords 1!"0!hydroxyalkyl#acrylonitriles "41# ð73SC0156Ł[ The reaction is e.cient "69Ð89)
isolated yield# for saturated aliphatic aldehydes\ but the same reaction with benzaldehyde yields
only 16) of the desired product[ It is believed that the reaction proceeds via the initially formed
betaine "42# which then reacts with the aldehyde to form "43# ð54JOC0246\ 69JOC2934Ł[ Elimination
of tri!butylphosphine from "43# gives the hydroxy substituted acrylonitrile "41#[
CN
+ + – CN
Bu3P – Bu3P
R CN
HO HO R
(52) (53) (54)
R2 R2
R2 TMS-CN, KCN, 18-crown-6 dbu
R1 O-TMS R1 O-TMS
R1
CHO
CN CN
(55)
dbu = 1,5-diazabicyclo[5.4.0]undec-5-ene
Scheme 17
O
R * CN
S CN
Ar * OH
(56) (57)
O R2
O
R1 LDA, THF HMPT
+ MeCN R1 CN
R2 R1 CN
R2
Cl OH
(58)
Scheme 18
R R
CN
O O O
(59) (60)
Ar OMe
NaH, DMF, 110 °C
ArCHO + MeO CN (15)
CN
1!Alkoxy!1!alkene nitriles can also be prepared from vinyl ethers[ In a one!pot\ three!step
sequence\ bromination of vinyl ethers followed by cyanide displacement leads to bromonitriles of
the type "50#[ Piperidine induced dehydrobromination then leads to the desired 1!alkoxy!a\b!alkenic
nitriles in 59Ð84) yield ð75S437Ł[ Scheme 08 is illustrative\ and the sequence is applicable to both
cyclic and acyclic vinyl ethers[ The aluminum chloride catalysed DielsÐAlder reaction between
a\b!unsaturated acyl cyanides and simple alkenes also gives 1!alkoxy!1!alkenic nitriles "Equation
"05## ð71AG"E#748Ł[ Acyl cyanides can also undergo a self!condensation reaction under mild\ basic
conditions to provide lactones of the type "51# ð72TL1736Ł[
Br N
i, Br2, CCl4 H
O ii, CuCN, ∆ O CN
O CN
(61)
Scheme 19
Bearin` an a\b!Vinylic Bond 542
AlCl3
+ (16)
O CN O CN
O O CN
(62)
Ph CO2Et
(63)
MeO2C CO2Me
HO CO2Me
(64) (65)
O R1 R1
N3
C6H6, 80 °C R2OH
N3 • O
R1 O NC
(66)
CO2R2 R1 CN
R2OH
•
R1 CN R2O CO2R2
(67) (68)
Scheme 20
R1 = Ph, Me
Scheme 21
O H H
NC
NC H NC H
(71) (72)
tributyl tin in THF results in an 78) yield of the corresponding g!phenoxy!a\b!unsaturated nitrile
"63# ð74JOC2447Ł[ The product is predominantly the E!isomer[ Interestingly\ the same reaction with
methoxytributyl tin provides only a 44) yield of the g!methoxy!a\b!alkenic nitrile ð74JOC2447Ł[
OAc OPh
Ph CN Ph CN
(73) (74)
O CN R1 CN
LDA, –78 °C
+ TMS (17)
R1 R2 SMe R2 SMe
(75)
O R1 CN
NC SMe Triton B or NaOEt
+ (18)
R1 R2 R2 SMe
R1 = alkyl, Ph, Ar; R2 = H, alkyl
Bearin` an a\b!Vinylic Bond 544
S CN CN
MeCN, BuLi MeI or CH2N2
Li+
R1 OR2 R1 S– R1 SMe
(76)
Scheme 22
Bromination of the a!thioether nitrile "66# leads to the bromothionitrile "67# "Scheme 12# which\
without isolation\ can be treated with triethylamine resulting in dehydrobromination to give the
corresponding a!ethylthio!a\b!unsaturated nitrile in 54Ð79) yield ð67TL1572Ł[ The eliminative
deoxygenation of a!cyanosulphoxides "68^ Ralkyl#\ by treatment with trimethylsilyl tri~ate in the
presence of hexamethyldisilazane\ leads to the a!thiophenyl!a\b!unsaturated nitriles "79# in excellent
yield "63Ð76)# ð74TL1284Ł[ a!Alkylthioacrylonitrile derivatives can also be prepared by the
rearrangement of a!chloro!b!alkylthionitriles induced by lithium bromide in N\N!dimethyl!
formamide ð45CB0152\ 63LA0550Ł[
R1 SEt Br2
R1 SEt Et3N
R1 SEt
Br
R2 CN R2 CN R2 CN
(77) (78)
Scheme 23
O
PhS R
Ph S R
NC
NC
(79) (80)
R1 R1 SR2
R2SNa, H2O
CN (19)
NC NC NH2
CN
NC SR CN
H2N SR
SR
NC SR NC
SR
(81) (82) (83)
The addition of thiols to allenylnitriles can also be used to prepare b!thio!a\b!alkenic nitriles[
Thus\ treatment of allenylnitriles "73^ R0 R1 alkyl# "Scheme 13# with thiols in the presence of a
catalytic amount of base gives the b!thio!b\g!alkenic nitriles "74# as a mixture of geometrical isomers
in excellent yields "89Ð84)# ð73T1030Ł[ Heating "74# at 199>C a}ords an equilibrium mixture of the
b!thio!a\b!alkenic nitrile "75# and the starting b\g!alkenic nitrile "74#\ although the latter constitutes
545 a\b!Unsaturated and Aryl Nitriles
only a minor "¼09)# portion of the mixture[ A similar equilibrium can be obtained by heating the
unconjugated nitrile "74# in ethanol in the presence of sodium ethoxide ð73T1030Ł[ Once again it is
the desired b!thio!a\b!unsaturated nitrile "75# which constitutes ca[ 89) of the equilibrium mixture[
R1
R1 CN R1 CN
R3–SH, EtO– heat or NaOEt
•
R2 CN
R2 R2 SR3
SR3
(84) (85) (86)
Scheme 24
O CN
PhSeCN, Bu3P
(20)
SePh
R R
Et3N R
Se CN
R
NC
NH2 CN
R N Se
H
R N Cl
(87) (88)
H2N
Se or NaHSe
H2N
Scheme 25
To this author|s knowledge\ there have been no reports of a\b!alkenic nitriles containing tellurium
substituents[
NC CN H 2N CN
NC CN R
(89) (90)
For the preparation of simple b!enaminonitriles "89#\ the most commonly employed method is
the dimerization of substituted nitriles[ The dimerization of acetonitrile with sodium metal in organic
solvent leads to "89^ RMe# in quantitative yield "ð42CJC0100\ 58AG"E#347\ 82CRV0880Ł and references
therein#[ The 0858 production also reports the synthesis of simple b!enaminonitriles\ in moderate
yield\ from the lithium aluminum hydride reduction of substituted malononitriles "Equation "10##
ð58AG"E#347Ł[
R CN R CN
LiAlH4
(21)
CN 40% NH2
The synthesis of a!amino!a\b!alkenic nitriles has received considerable attention "ðB!72MI 208!90Ł
and references therein#[ One common method for access into this class of compound involves
deprotonation of saturated a!aminonitriles with strong base ð59JA0675\ 56CC107Ł[ Alternatively\
deprotonation of "80# with lithium diisopropylamide in THF at −67>C followed by silylation\ base
treatment and exposure to formaldehyde\ yields the desired a!amino!a\b!alkenic nitrile in 64) yield
"Equation "11## ð67S786\ 68S016Ł[ Another popular method for the synthesis of a!cyanoenamines
involves cyanation of enamines themselves ðB!72MI 208!90Ł[ In one example\ reaction of an enamine
with cyanogen bromide a}ords the b!cyanobromide "81#\ which upon exposure to triethylamine\
eliminates hydrogen bromide to give the desired a!amino!a\b!unsaturated nitrile "Scheme 15#
ð66S384Ł[
CN CN
i–iv
(22)
N Ph N Ph
Me Me
(91)
i, LDA; ii, TMS-Cl; iii, LDA; iv, H2CO
Scheme 26
O PhSO2Na
X i, Me2SO4 CN
Scheme 27
547 a\b!Unsaturated and Aryl Nitriles
The g!phenylsulphonyl!a!cyanoenamine "83#\ in the presence of a strong base\ acts as a synthetic
equivalent of an a!carboxyl vinyl anion ð73TL2364Ł[ Exposure of an aldehyde to an amine\ followed
by chlorination and subsequent treatment with potassium cyanide also gives a!amino!a\b!alkenic
nitriles "Equation "12## ð68S630Ł[
i, R3NH2
R1 O
ii, NCS
R1 NHR3
(23)
iii, KCN CN
R2 R2
ButN NBut
OR2 NBut R2O NHBut
ButNC, TiCl4 ButNC
R1 R1
R1
OR2 OR2 R1 CN
OR2
(95) (96)
R1 = H, alkyl, Ph; R2 = Me
Scheme 28
R1 NBut
R3
R2O CN
(97)
R1 CN R1 CN
HNR22, CCl4
(24)
Br R22N
(E)
The nucleophilic displacement of vinyl halides with cyanide ion also proceeds in high yield[
Thus\ exposure of the vinyl bromide "87# to potassium cyanide in dimethyl sulfoxide gives the
b!amino!a\b!alkenic nitrile "88# ð62S098Ł[ Compounds of the type "88# have also been prepared by
using phase!transfer catalysis ð67S781\ 67S783Ł[
Br NHAr3 NC NHAr3
(98) (99)
The reaction of carbonyl compounds under Wittig conditions has been successfully employed in
the synthesis of b!amino!a\b!alkenic nitriles[ Thus\ treatment of succinimides with cyano!
methylenetriphenylphosphorane gives the corresponding 1!cyanomethylene!4!pyrrolidones "099# in
Bearin` an a\b!Vinylic Bond 548
poor to moderate yields "12Ð59)# ð60CB1736Ł[ The best result "59) yield# occurs with succinimide
itself "RH#\ whilst the yields fall substantially with any substitution on the nitrogen[
CN
O N
R
(100)
b!Amino!a\b!unsaturated nitriles can also be prepared via the decarboxylation of enamino esters[
Whilst it has been reported that enamines like "090# can be formed by the treatment of enamino
esters "091# with aqueous base ð58AG"E#232\ 65CPB2900Ł\ the same reaction with cyanoesters of the
type "091^ ZCN# results in a retro!condensation to give a pyrrolidinone and ethyl cyanomalonate
ð70JOC2560Ł[ This problem has been overcome by heating cyanoesters of the type "091^ ZCN^
R0 Me\ H^ R1 H# at high temperature "199Ð149>C# with acidic alumina for 0 h "Equation "14##[
This transformation is highly temperature dependent ð74SC362Ł[
RO2C
N R2 N R2
Z R1 Z R1
(101) (102)
2[08[1[7 a\b!Alkenic Nitriles with P!\ As!\ Sb! and Bi!based Substituents
There are very few publications detailing the synthesis of a\b!alkenic nitriles containing P!\ As!\
Sb! and Bi!based substituents[ Indeed\ apart from reports on the preparation of a\b!unsaturated
nitriles with phosphorus substituents\ it appears that a\b!alkenic nitriles with arsenic\ antimony or
bismuth!based substituents are unknown[
In one report\ detailing the preparation of 1!cyano!0\2!butadienes "Section 2[08[1[1\ ð72S806Ł#\
diethyl 1!lithio!1!cyano!1!trimethylsilylethanephosphonate "092# is condensed with an aldehyde to
give the 1!cyano!1!alkenephosphonate "093# "Equation "15##[ Whilst the cyanophosphonate "093# is
highly reactive and usually reacts in situ\ it has been isolated in moderate yield[
O
O Li R
TMS R O
(EtO)2P (26)
CN –78 °C (EtO)2P
CN
(103) (104)
O CN
O (EtO)2P CN O
CN, LiCN R
O O P(OEt)2
R P R O
EtO OEt
(105) (106)
Scheme 29
559 a\b!Unsaturated and Aryl Nitriles
from a\b!alkenic ketones whilst the E!isomer of "095# predominates when a!b!alkenic aldehydes are
used[ The high Z!stereospeci_city in the former case can be explained by considering the ð2\2Ł!
sigmatropic rearrangement of the low energy conformer of the initially formed "094# ð75CPB3519Ł[
R1 CN
TMS R1 CN i, Bun4NF
TMS CN R1–CHO
• N-TMS
ii, R2COR3 R2
TMS TMS
HO R3
(107) (109) (108)
Scheme 30
The exposure of an arylalkyne "009# to trimethylsilyl cyanide in the presence of catalytic palladium
chloride and pyridine results in the addition of triethylsilyl cyanide across the carbonÐcarbon triple
bond to give b!cyano!b!arylalkenylsilanes of the type "000# "Equation "16## ð74CC727Ł[ The addition
of the trimethylsilyl cyanide stereoisomer proceeds with high regio! and stereoselectivity to give the
product "000# in generally high yield "up to 89)#[ As an aside\ the addition of trimethylsilyl cyanide
to allenes\ under either palladium or nickel catalysis\ gives E! and Z!isomeric mixtures of the
corresponding b!trimethylsilyl!b\g!unsaturated nitriles "001# ð75TL0730Ł[
Ar
PdCl2, pyridine
Ar + TMS-CN (27)
NC TMS
(110) (111)
R TMS
CN
(112)
HCN, Ni0
R13Si R2 R13Si R2
R13Si R2 + (28)
CN NC
(113) (114)
R2 = H, Me, Bu, Ph
Reports detailing the synthesis of a\b!alkenic nitriles containing boron!based substituents have
not appeared[
Bearin` an a\b!Aryl 550
2[08[1[09 a\b!Alkenic Nitriles with Metal Substituents
a\b!Alkenic nitriles with metal substituents are highly reactive species and as such have not been
isolated[ Such species are therefore considered as transient intermediates and will not be discussed
here[ However\ it is worth remembering that such species\ formed by deprotonations of
a\b!unsaturated nitriles with strong base\ are valuable intermediates in the preparations of sub!
stituted a\b!alkenic nitriles "ðB!72MI 208!90Ł and references therein#[
Furthermore\ several reviews ðB!69MI 208!90\ B!72MI 208!90\ B!72MI 208!91\ 80COS"5#114Ł provide an
excellent introduction to the synthesis of aromatic nitriles in general\ and readers interested in this
topic are urged to consult these comprehensive articles[ Once again\ space limitations dictate that
this section focuses on general strategies towards the synthesis of aryl and hetaryl nitriles\ and in
particular on developments since 0874 in the synthesis of such compounds[
The substitution of a halide by cyanide ion is the most common route into a\b!aryl nitriles
ð76CRV668Ł[ Indeed\ the preparation of aromatic nitriles by the substitution of a variety of functional
groups is the favoured method of many workers ðB!72MI 208!91Ł[ As detailed above\ the direct
cyanation of aromatic halides with copper"I# cyanide requires relatively forcing conditions "049Ð
149># ð76CRV668Ł[ In an attempt to carry out this transformation under far milder conditions\
several researchers have investigated the use of complexes of sodium or potassium cyanide with
transition metals or metal!triphenylphosphine ð76CRV668Ł[ It is considered that reactions with such
metal complexes proceed as illustrated in Scheme 20\ and may involve an oxidative one!electron
transfer ð60JOM"17#176Ł[
–CN
Ar X + M Ar M X Ar CN + M + X–
Scheme 31
Complexes of palladium and nickel are particularly useful for this reaction[ For example\
reactions of an aryl halide with sodium cyanide in the presence of tris"triphenylphosphine#nickel"9#
"Equation "29## in either methanol\ ethanol or acetone at 29Ð59>C give the corresponding a\b!aryl
nitriles in excellent yield "×89)# ð62JOM"43#C46Ł[ Other nickel catalysts\ including trans!chloro!
bis"triphenylphosphine#nickel "NiCl1"PPh2#1# have also been used and provide aryl nitriles in excel!
lent yields "×79)# ðB!63MI 208!90\ 68JOM"062#224\ B!72MI 208!90\ 76CRV668Ł[ Similarly\ conversions of
chloro! and iodoaryl compounds into aryl cyanides have been achieved in 71Ð80) yield using
tetrakis"triphenylphosphine# palladium"9# and potassium cyanide in re~uxing THF ð64CL166Ł[
Ni(PPh3)3
X + NaCN CN (30)
R R
X = Cl, Br, I
In an adaptation of these transition metal catalysed aromatic cyanations\ it has been found that
the reactions of aryl iodides with trimethylsilyl cyanide and catalytic tetrakis"triphenylphosphine#
palladium"9# in triethylamine at re~ux provide the corresponding a\b!aryl nitriles in high yield
"Equation "20## ð75JOC3603Ł[ Under these conditions both aryl bromides and aryl chlorides fail to
551 a\b!Unsaturated and Aryl Nitriles
react[ Catalysis of aryl iodide displacement by palladium"II# salts\ especially palladium"II# acetate\
also results in high yields of aryl nitriles ð64BCJ2187Ł[ Aryl halides also react with palladium"II# salts
in the presence of sodium cyanide on alumina giving aryl nitriles in excellent yield ð68JOC3332Ł[
Various cobalt complexes have also been used to catalyse the aromatic substitution of a halide with
a nitrile ð72JOM"132#84\ 76CRV668Ł[
Pd(PPh3)4, Et3N
I + TMS-CN CN (31)
R R
R = H, Me, Br, Cl, MeO, MeO2C
It must be remembered that in all these metal catalysed substitution processes\ the nature and
position of other substituents on the aromatic ring has an e}ect on the outcome of the reaction
ð76CRV668\ 80COS"5#114Ł[ In general terms\ the aromatic ring may carry various substituents "but not
nitro groups because of the interaction between the nitro group and the metal catalyst#\ although
ortho!substituents tend to give rise to lower yields of the corresponding a\b!aryl nitriles ð76CRV668Ł[
Functional groups other than halogens\ including oxygen\ hydrogen\ nitrogen and organometallic
groups\ may also be substituted by cyanide ion ðB!72MI 208!90\ B!72MI 208!91Ł[ Examples of these less
commonly used\ but nevertheless important\ transformations will be presented in the following
section "see 2[08[2[1#[
The preparation of aromatic nitriles via elimination reactions is perhaps the other general synthetic
approach towards these compounds[ The dehydration of oximes "Equation "21## is by far the most
common of these elimination reactions\ and several reagents have been used ðB!72MI 208!91Ł[ For
example\ the {phosphonium anhydride| species "004# resulting from the reaction of two equivalents
of triphenylphosphine oxide with one equivalent of tri~ic anhydride\ dehydrates aryl oximes to aryl
nitriles in 4 min at room temperature in ×89) yield ð76JOC3026Ł[
N OH –H2O
Ar CN (32)
Ar
OTf
Ph3P
O
Ph3P
OTf
(115)
The direct transformation of aryl aldehydes into nitriles via the oxime may be performed with a
variety of reagents ðB!72MI 208!91Ł[ In one report with several examples of the preparation of
substituted benzonitriles from the corresponding aldehydes ð63CB0110Ł\ the intermediate oxime is
not isolated but treated with dicyclohexylcarbodiimide in the presence of copper"II# ions and
triethylamine[ The yields are excellent for this transformation "×69)#[ Similarly\ the conversion
of aromatic aldehydes into aryl nitriles can be achieved using ortho!"1!aminobenzoyl#hydroxylamine
and BF2 = OEt1 "Scheme 21# ð77SC1068Ł[
–
+ BF3
COONH2 O
BF3•OEt2, EtOH
+ Ar CHO N Ar Ar CN
O
NH2
NH2
Scheme 32
Scheme 33
Ar
N
O Et3N O– Cl–SO2–NCO Et3N
O H
Ar CN
Ar NH2 Ar NH N–
O S Cl
O2
(117)
Scheme 34
Beckmann fragmentation of ketoximes "Scheme 24# ðB!72MI 208!91Ł[ The requirement for this
fragmentation to succeed is that the substituent on the a!carbon "A# must be able to stabilize\ or
bear\ a positive charge[ This fragmentation is often performed using thionyl chloride\ as exempli_ed
by the transformation shown in Scheme 25 ð62JA1812Ł[ Despite some conjecture as to the role of
sulfur in this particular case ð57JA3813Ł\ it is believed ð62JA1812Ł that the sulfur is capable of
stabilizing the adjacent cation in the intermediate "007#[ Similarly\ the Beckmann fragmentation of
b!trimethylsilylketoximes\ e[g[\ "008# "Equation "22##\ catalysed by boron tri~uoride etherate\ pro!
vides the corresponding aryl nitrile in 84) yield ð77T1302Ł[
Ar Ar
N OH N X Ar CN
A A
Scheme 35
OH
N CN CN
SOCl2, C6H6, RT SOCl2
S +
S Cl
S
(118)
Scheme 36
OAc
N CN
BF3•Et2O
(33)
TMS
(119)
Rearrangement reactions can also be used to prepare aryl nitriles\ although less frequently than
the substitution or elimination processes detailed above[ The simplest of such rearrangements is
that involving the isothiocyanide to nitrile transformation ð68COC"1#417Ł\ which occurs irreversibly
at temperatures above 049>C "Scheme 26#[
(PhO)3P
Ar N C S Ar N : Ar CN
Scheme 37
553 a\b!Unsaturated and Aryl Nitriles
2[08[2[1 Benzonitrile and Substituted Benzonitriles
The substitution of various functional groups\ especially halides "Section 2[08[2[0#\ by cyanide
ion is the most widely used method for the preparation of benzonitriles[ The substitution of diazo
groups by cyanide ion\ _rst reported by Sandmeyer in 0773 ð0773CB0522Ł\ represents an important
route into aryl nitriles "Equation "23## ð80COS"5#114Ł[ The many reports of this transformation vary
mainly in the type of copper cyanide complex employed ð80COS"5#114Ł[ In a modi_cation of this
general approach\ treatment of aromatic diazo sul_des with tetrabutylammonium cyanide leads to
the corresponding benzonitriles ð76T3514\ 89T1194Ł[
[CuCN], ∆
Ar N2+ Ar CN (34)
The boron trichloride mediated cyanation of anilines with trichloroacetonitrile or with methyl!
thiocyanate "Scheme 27# gives ortho!cyanoanilines in moderate yield after basic workup ð89SC60Ł[
Similarly\ phenols undergo this same FriedelÐCrafts type reaction to give ortho!cyanophenols in
60Ð77) yield ð89SC60Ł[
H
NH2 N NH2
MeSCN, BCl3 BCl base
N CN
R R R
SMe
Scheme 38
NO2 NO2
NO2 OH
CN
KCN, DMSO, 3 h, 100 °C
(36)
COPh COPh
The displacement of aromatic organometallic groups by cyanide ion has also been employed to
good e}ect in the synthesis of benzonitriles[ Thus\ electrophilic thallation of aromatic substrates
with thallium tris"tri~uoroacetate# "Scheme 28# followed by exposure to copper"I# cyanide in aceto!
nitrile leads to various aryl nitriles in good to excellent yield "42Ð73)# ð73TL4362Ł[ The reaction is
believed to proceed via an initial one!electron transfer from Cu"I#\ producing an unstable Tl"II#
species which then undergoes homolysis of the carbon to thallium bond leading to an aryl radical
"Scheme 28# ð73TL4362Ł[ Similar organometallic displacement reactions have been performed on
arylthallium acetate substrates with copper cyanide in pyridine ð61T2914Ł\ and an aryltin species
with cyanogen chloride ð61JOM"35#156Ł[
Another substitution process involving metallated aromatic compounds involves the reaction of
benzylic organozinc halides with tosyl cyanide "Equation "26##[ The transformation is completely
Bearin` an a\b!Aryl 554
R R
R R
Scheme 39
regioselective\ can tolerate a variety of other functional groups\ and produces benzonitriles in 56Ð
64) yield ð82TL3512Ł[
ZnBr TsCN
R (37)
R 67–75%
CN
Alternatively\ metallated alkyl nitriles can be used in the preparation of benzonitriles[ Thus\
addition of a!lithioalkyl nitriles to the benzyne derived from aryloxazolines results in cyclization to
give the benzocyclobutanone imine "019# which then fragments to give 1!alkyl!2!cyanobenzoic acids
in high yield "Scheme 39# ð73TL1830Ł[
Oxz
Oxz Oxz R R
Li R
EtOH
+ CN
CN
N
Li
Li
(120)
Oxz CO2H
hydrolysis
R R
CN CN
Scheme 40
The substitution of alkoxy groups by cyanide can be achieved by the anodic oxidation of
cyanide!ion solutions containing alkoxy substituted aromatic substrates ð58JA3070\ B!72MI 208!91Ł[
Electrooxidation of 1\1\5\5!tetramethylpiperidinyl!0!oxy "TEMPO# forms the nitrosonium ion "010#
which reacts with benzylic amines to give the intermediate imine "011# "Scheme 30#[ The imine "011#
then reacts with a further nitrosonium ion "010# to give various benzonitriles "68Ð80) yield#
ð72JA5621Ł[ Benzylic amines can also be oxidized directly to benzonitriles in moderate yield "24Ð
30)# with copper"I# chloride and oxygen in the presence of pyridine ð66S134Ł[
+
N
O
+ + Ar NH2 Ar NH Ar CN
N
O
(121) (122)
Scheme 41
The preparations of benzonitriles from carbonyl compounds or their derivatives o}er many
alternative strategies ðB!72MI 208!91Ł[ The addition of trimethylsilyl azide to aromatic aldehydes in
the presence of zinc chloride gives the corresponding benzonitriles in 51Ð86) yield ð73CL662Ł[
Aromatic carboxylic acids can be converted directly into the corresponding nitriles with reagents
such as aminosulphonic acid and urea\ or with methanesulphonamide and phosphorus pentachloride
555 a\b!Unsaturated and Aryl Nitriles
ðB!72MI 208!91Ł[ Chlorosulphonyl isocyanate reacts with carboxylic acids to give N!chloro!
sulfonamides "Scheme 31# which decompose to nitriles in N\N!dimethylformamide ð56CB1608Ł[
MeO OMe
MeO OMe MeO OMe
ClSO2NCO H DMF
N
SO2Cl
CN
O
Scheme 42
Amides are also a common source of benzonitriles ðB!72MI 208!91Ł[ The thermal decomposition
of aryl amides in the presence of a catalyst above 149>C leads to benzonitriles ð69JOC2142\ 69TL0852Ł[
A series of substituted aryl nitriles have been prepared by the reaction of aromatic N!methoxy
amides with carbon tetrachloride or carbon tetrabromide and triphenylphosphine in acetonitrile to
give the intermediate N!alkoxyimidoyl halides "012^ XCl\ Br# "Scheme 32#\ which on exposure to
zinc in acetic acid a}ord the desired benzonitriles in generally excellent yield ð80S649Ł[ Similarly\
aryl N!hydroxyimidoyl chlorides lead to aryl nitriles upon exposure to the hydridoundeca!
carbonyltriferrate anion ðHFe2"CO#00Ł− in benzene at re~ux ð62JOC3254Ł[
O X
CX4, Ph3P, MeCN Zn, AcOH, DMF
OMe OMe Ar CN
Ar N Ar N
H
(123)
X = Cl, Br
Scheme 43
N CN
OR CN
NaH, DMF
+ RONa
NO2 NO2 OR
Scheme 44
Other nitrogen containing functional groups which can be converted into nitriles include the
oxidation of aromatic hydrazones "Scheme 34# ð55JOC3099Ł and the preparation of benzonitriles by
the ring cleavage of heterocycles ðB!72MI 208!91Ł[ In the latter case\ mainly _ve! and six!membered
nitrogen heterocycles are used as substrates\ and oxidative\ thermal and photochemical processes
are usually involved ðB!72MI 208!91Ł[ For example\ lead tetraacetate oxidation of the triazole "013#
"Scheme 35# gives the corresponding nitrene "014# which then eliminates molecular nitrogen to
produce two moles of benzonitrile ð69TL2740Ł[
Ar
Ar 30% H2O2 N
+ Ar CN
NNMe2 NMe2
–O
Scheme 45
Bearin` an a\b!Aryl 556
N N N N
Pb(OAc)4 –N2
Ph N Ph Ph N Ph 2PhCN
NH2 :N:
(124) (125)
Scheme 46
Cycloaddition reactions can also be used to prepare benzonitriles[ In one example\ the ð3¦1Ł!
cycloadduct "015# eliminates hydrogen cyanide leading to various substituted biaryl!1!carbonitriles
in 54Ð79) yield "Scheme 36# ð89JOC1434Ł[
CN CN
CN
C6H6 –HCN
+ NR2 CN
Ar CN Ar
Ar
(126)
Scheme 47
Ph NC NC
Ph Ph
–CN [O]
Ph Ph Ph
Ph Ph Ph
(127)
Scheme 48
The addition of cyanide ion to carbonyl compounds is also a convenient route into aromatic
nitriles[ Reaction of 8!benzoylanthracene with sodium cyanide at 79>C in N\N!dimethylformamide
followed by the addition of a mild oxidant leads to 8\09!dicyanoanthracene ð62JOC370Ł[ Alter!
natively\ the reaction between 5!methoxytetralone and trimethylsilyl cyanide in the presence of
catalytic boron tri~uoride a}ords the cyanohydrin derivative "017# "Scheme 38# ð72JOC4023Ł[
Exposure of "017# _rstly to phosphoryl chloride in pyridine and then to aromatization conditions
"09) palladium on carbon with sulphur# then gives the aryl nitrile "018#[ Similarly\ the bis"trimethyl!
silyl cyanohydrin# "029#\ obtained by the addition of trimethylsilyl cyanide to the corresponding
diketone\ upon exposure to phosphoryl chloride in pyridine leads to the biscyano aromatic com!
pound "020# ð68CL0316Ł[
The use of nitrogen based precursors is also a common avenue into polycyclic aromatic nitriles
"see Section 2[08[2[1#[ The reaction of aromatic diazosul_des with tetrabutylammonium cyanide
under photolytic conditions furnishes dicyanonaphthalenes in good yield ð89T1194Ł[ The photo!
induced cyanide ion displacement of aryl nitro groups "Equation "27## a}ords moderate yields of
the corresponding aryl nitrile compounds ð69TL3690Ł[
557 a\b!Unsaturated and Aryl Nitriles
O NC O-TMS CN
TMS-CN, BF3 i, POCl3, pyridine
ii, Pd on C, S
MeO MeO MeO
(128) (129)
Scheme 49
CN
NC O-TMS
NC O-TMS
CN
(130) (131)
NO2 CN
hν, –CN
(38)
The thermal\ potassium hydroxide!induced ring opening of the bis"tosylhydrazone# "021# gives
0\7!dicyanonaphthalene in moderate yield ð79CC680Ł[ Pyrolysis of the 0\1\4!thiadiazole!0\0!dioxide
"022# results in the extrusion of sulfur dioxide with concomitant ring cleavage to provide the bis
aryl nitrile "023# ð63S11Ł[
TsN N N NTs
N O CN
S
O CN
N
Treatment of aryl substituted acetamides with a hypochlorite liquid triphasic system results in
the loss of one carbon via a Hofmann rearrangement "Equation "28## producing aryl nitriles in
moderate yield ð83S0016Ł[
NH2 CN
NaOCl, NaBr, TBAHSO4
(39)
O benzene, H2O, Na3PO4
The reaction of bianthrone with malononitrile in pyridine a}ords the extensively conjugated
18\18\29\29!tetracyanobianthraquinodimethane "TBAQ# "024# in 61) yield ð75TL1300Ł[ TBAQ was
prepared as part of a study aimed at developing new electron acceptors with enhanced conductivity
"see for example ð73NAT008Ł#[
NC CN
NC CN
(135)
Bearin` an a\b!Aryl 558
Cycloaddition reactions also provide a route into polycyclic aromatic nitriles[ Condensation
between the benzylic nitrile "025# and the diene "026# in the presence of a base at elevated tem!
peratures gives rise to the polycyclic aromatic nitrile "027# "Equation "39## ðB!72MI 208!90Ł[ Acry!
lonitrile itself can act as the dienophile in cycloaddition reactions[ Thus\ reaction between "028# and
acrylonitrile in tetrahydrofuran at re~ux gives the aryl nitrile "039# after aromatization of the
intermediate adduct "Scheme 49# ð61JCS"P0#1943Ł[
Me
CN ClO4– CN
N+
Me base
+ (40)
i, 50–70 °C
R ii, 145–205 °C R
NMe2
(136) (137) (138)
Me
O
O– N Me2N
THF, reflux O i, MeI, EtOAc
+
+ CN ii, Ag2O, H2O
N CN
Me
NC
(139) (140)
Scheme 50
Apart from the displacement of a heteroaryl halide with cyanide ion ð76CRV668Ł there are other
methods involving a variety of reagents for the direct cyanation of heterocyclic aromatic substrates
ð68H"01#708\ B!72MI 208!90Ł[ The cyanation of pyrrole with triphenylphosphineÐthiocyanogen complex
"Equation "30## a}ords 1!cyanopyrrole in 79) yield ð79JCS"P0#0021Ł[ Cyanation of indoles can also
be achieved with this reagent ð79JCS"P0#0021Ł\ although only if there are no electron!withdrawing
groups on the indole ring[ Indoles can also be cyanated with the powerful electrophile chlorosulfonyl
isocyanate ð67S263Ł[ This same reagent has also been used for the cyanation of pyrroles ð70CJC1562Ł\
thiophenes ð69OS"49#41Ł and furans ð72T2770Ł[ Moderate to excellent yields of the corresponding
heteroaryl nitriles are obtained in all of these examples[ The reaction proceeds through a chloro!
sulfonyl carboxamide intermediate\ such as "031# in the pyrrole series\ which liberates HCl and
SO2 upon the addition of N\N!dimethylformamide ð70CJC1562Ł[ Importantly\ the nature of other
569 a\b!Unsaturated and Aryl Nitriles
substituents on the heterocyclic ring can alter the position of cyanation[ Thus\ if a deactivating
group is in the 1!position of pyrrole "e[g[\ 1!carboxyaldehyde# the product is the corresponding
3!cyanopyrrole ð70CJC1562Ł[ Several examples of 1!substituted furans "032^ RH\ Me\ CH1OH\
CH1OAc\ CH1OMe# give 4!cyanofurans upon exposure to chlorosulfonyl isocyanate ð72T2770Ł[ If
1\4!disubstituted furans are employed then 2!cyanofurans result ð72T2770Ł[
CH2Cl2, –40 °C
+ Ph3P(SCN)2 CN (41)
N N
H H
H
N
N SO2Cl R
H O
O
(142) (143)
R = H, Me, CH2OH, CH2OAc, CH2OMe
Diethyl phosphorocyanidate in the presence of lithium cyanide reacts with 2!acylindoles "033# to
a}ord 1!cyano!2!indoleacetonitriles in excellent yield "Scheme 40# ð75CPB3434Ł[ In the several exam!
ples reported\ either R0 or R1 is hydrogen[ Indeed 0!methyl!2!acetylindole "033^ R0 R1 Me# is
recovered unchanged when exposed to these conditions[
O O NC
R2 O R2 CN R2
O P(OEt)2
(EtO)2P
CN
LiCN CN
–CN
N N N
R1 R1 R1
(144)
NC
R2
CN
N
R1
R1 = H, Me, Et, Ph, CH2Ph; R2 = H, Me, Ph
Scheme 51
The reaction of aryl organozinc halides with p!toluenesulphonyl cyanide leading to aromatic
nitriles has already been mentioned "Section 2[08[2[1#[ The same article ð82TL3512Ł also reports that
various heteroaryl organozinc iodides "indoles\ thiophenes\ benzothiazoles# a}ord the corresponding
nitriles in high yield under the same conditions[
1!Cyanoergolines "034# have been prepared by the electrochemical cyanation of ergolines in
moderate yield "30Ð37)# ð72TL1730Ł[ The reaction is performed in methanolic aqueous sodium
cyanide solution using a platinum electrode[
R2
N Me
H H
N CN
R1
(145)
Bearin` an a\b!Aryl 560
Trimethylsilyl cyanide is a valuable reagent in the preparation of heteroaryl nitriles[ For example\
treatment of pyridine N!oxide with trimethylsilyl cyanide in the presence of triethylamine in aceto!
nitrile a}ords 1!cyanopyridine in high yield "Scheme 41# ð72S205Ł[ Only traces of 3!cyanopyridine
are reported from this reaction[ This modi_cation of the ReissertÐHenze reaction can be performed
on a variety of substituted pyridine N!oxides\ including alkyl\ hydroxy\ carboxy and carboxamido
groups[ Quinoline N!oxides also react under these conditions to give 1!cyanoquinoline[ The same
transformation can also be carried out with trimethylsilyl cyanide in the presence of dimethyl!
carbamyl chloride\ resulting in excellent yields "83Ð099)# of substituted 1!cyanopyridines
ð72JOC0264Ł[ The reaction is believed to proceed as depicted in Scheme 42 ð72JOC0264\ 80COS"5#114Ł[
Scheme 52
O + +
CN
N TMS-CN N –Me2NH, –CO2
N + H
Me2N Cl O NMe2 O NMe2
O
O O
N CN
Scheme 53
Trimethylsilyl cyanide also reacts with alkynes in the presence of a palladium or nickel catalyst
leading to 1!cyano!4!aminopyrroles "Equation "31## ð75TL3190Ł[ Diarylacetylenes "035^ RAr# give
the corresponding cyanopyrroles in 64Ð76) yield\ whilst arylalkynes "035^ RH# a}ord only
moderate yields of cyanopyrroles[
R Ar
PdCl2 or NiCl2
Ar R + TMS-CN (42)
(146) NC N N(TMS)2
H
R = Ar, H
Other metal catalysts can also be employed in heteroaryl nitrile synthesis[ Thus\ exposure of
a!hydrazononitriles "e[g[\ "036## to anhydrous aluminum chloride produces 3!amino!2!cyano!
cinnoline "037# ð76H386Ł[
NH2
CN
CN
PhNH N
CN N
N
(147) (148)
Carbonyl compounds have been widely used as substrates in the synthesis of heterocyclic aromatic
nitriles[ In one example\ reaction of o!phthalaldehyde with primary amines\ followed by the addition
of potassium cyanide gives 0!cyano!1!substituted!isoindoles in moderate to excellent yield "Scheme
43# ð74CL0376Ł[ o!Hydroxybenzaldehyde undergoes a Knoevenagel condensation with malononitrile
on an AlPO3ÐAl1O2 catalyst in the absence of solvent to produce the benzopyran "038# via the
initial intermediate "049# "Scheme 44# ð73JOC4084Ł[ Similarly\ a!hydroxyketones condense with
malononitrile to produce furan derivatives ð76H386Ł[
561 a\b!Unsaturated and Aryl Nitriles
H
CHO i, NaHSO3 (aq.) CN CN
ii, RNH2
N R
iii, KCN N R
CHO CN
H
Scheme 54
OH CN OH
AlPO4-Al2O3 CN
+
CHO CN CN
(150)
O NH O O
H3O+
CN CN
(149)
Scheme 55
Diketones or their derivatives are also valuable substrates in heteroaryl nitrile synthesis[
a!Chloroacetylacetone reacts with malononitrile to a}ord the cyanofuran "040# ð51CB170Ł\ whilst
1!acylcyclohexanones react with cyanoacetamide in diethylamine leading to a mixture of the cyano!
isoquinoline "041# and the cyanoquinoline "042# ð76H"15#386Ł[ The oximino ketone "043#\ prepared
from the enol ester "044# "Scheme 45#\ upon exposure to thionyl chloride leads to the 1!cyano!
imidazole "045# ð62JHC788Ł[ Similarly\ the 1!cyanobenzimidazole "046# results from thionyl chloride
induced fragmentation of the corresponding oximino ketone ð62JHC788Ł[ The imidazole derivative
"045# can also be prepared by the mild thermal decomposition of the oximino pyruvate "047#
ð62JHC788Ł[
CN
O R
CN OH
CN
N
O NH2 N OH
R
(151) (152) (153)
O
Ph O
N
O N Ph
HOSO2NO2 SOCl2 CN
N Ph
O2N N
O2N N NOH
Me
O2N N Me
Me
(155) (154) (156)
Scheme 56
O OEt
N
N
CN
O
N
O2N N N OH
R
Me
(157) (158)
Bearin` an a\b!Aryl 562
Glyoxal a!oximes have also been used as precursors to cyano substituted imidazoles[ In a three!
step procedure the nitroimidazole "048# is reacted with dimethylformamide dimethyl acetal leading
to the enamine "059# which on exposure to sodium nitrite in acetic acid gives the glyoxal a!oxime
"050# "Scheme 46#[ Tri~uoroacetic anhydride treatment of "050# then a}orded 3!cyano!0!alkyl!4!
nitroimidazole "051^ Ralkyl# ð74JOC4781Ł[ Similarly prepared was the isomeric 4!cyano!0!alkyl!
3!nitroimidazole "052#\ and in both instances the chemical yields were high for each step in the
sequence ð74JOC4781Ł[
N Me2N
N
Me2NCH(OMe)2, H+ NaNO2, AcOH, H2O
O 2N N N
O2N
R R
(159) (160)
OH
N NC N
OHC N
O 2N N
O2N N R
R
(161) (162)
R = alkyl
Scheme 57
R
NC N
O2N N
(163)
3!Cyanoimidazoles "053# have also been prepared by exposure of the corresponding 3!"tri~uoro!
methyl#imidazole to dilute ammonium hydroxide solution "Scheme 47# ð75JOC2117Ł[ The yields for
a variety of substituted cyanoimidazoles "053^ Rheteroaryl# prepared in this way are generally
excellent[
F
F3C N NC N
NH4OH
R F N R
N R N
N
H H
(164)
Scheme 58
N
CN N CN
N N N3 N
OH OH
O
(165) (166) (167)
563 a\b!Unsaturated and Aryl Nitriles
SO2Ph SO2Ph
SO2Ph
CN
: :
NaN3, DMF N N N
X
N N
N
R H
R R
(170)
(168) CN
R
N
H
(169)
X = Cl, SO2Ph
Scheme 59
O O
R CN NC CN
H 2N NH2
(171) (172) (173)
Chlorination of acrylonitrile and pyrolysis of the resulting dichloro intermediate "063# "Scheme
59# leads to a!cyanoalkyne itself in 39) yield ð69JOC564Ł[ Similarly\ pyrolysis of the trichloro!
acrylonitrile derivative "064# at 899>C gives the b!chlorocyanoalkyne "065# in 64) yield ð69JOC564Ł[
Cl2 CN
Cl 1000 °C
CN CN
Cl
(174)
Scheme 60
CN
Cl Cl CN
Cl
Cl
(175) (176)
The pyrolysis of b!ketoalkylidenetriphenylphosphoranes of the type "066# under far milder con!
ditions "119>C# also provides a route to a\b!alkynic nitriles "067# ð51JCS1222Ł[ The phosphoranes
"066# can be prepared conveniently by the reaction of cyanomethylenetriphenylphosphorane with
acid chlorides[ This procedure was later extended to include the preparation of dialkynic nitriles
ð53JCS432Ł[ Thus\ pyrolysis of the b!ketoalkylidenephosphorane "068#\ this time prepared by the
reaction of the corresponding a\b!alkynic acid chloride with cyanomethylenetriphenylphosphorane\
at 179Ð299>C furnishes dialkynic nitriles of the type "079# "Equation "32##[
Bearin` an a\b!Triple Bond 564
R CN
+
R CN
–O PPh3
(177) (178)
CN
Ph3P 280–300 °C
NC R (43)
R
O
(179) (180)
In 0882 a novel synthesis of a\b!alkynic nitriles was published ð82TL4800Ł involving the iodine!
catalysed cyanation of terminal alkynes with cuprous cyanide "Equation "33##[ The yields for this
transformation are generally good to excellent "42Ð73)# with the best results when Raryl
"Equation "33##[ Importantly\ the authors found that the use of dimethyl sulfoxide with acetonitrile
in the ratio of 2 ] 0 was the ideal solvent system for this reaction\ with di}erent proportions of these
two solvents or other solvents "e[g[\ THF\ THF and HMPA\ benzene# resulting in signi_cantly
lower yields of the desired a\b!alkynic nitriles[
R = aryl, alkyl
Terminal alkynes can also be transformed into a\b!alkynic nitriles via reaction with copper
cyanide in the presence of bis"trimethylsilyl#peroxide "Equation "34## ð80TL1058Ł[ It is believed that
the reaction involves a formal transfer of CN¦ from CuCN to the terminal alkyne in an umpolung
fashion via the intermediate hypo species TMS0O0CN ð80TL1058Ł[
R
TMS-O O-TMS + CuCN R CN (45)
THF
The reaction of metallated alkynides with cyanogen chloride to furnish a\b!alkynic nitriles is a
classical method for the preparation of these compounds ð04BSF117\ 15AC"P#4\ 62RTC556Ł[ An obvious
problem with such an approach is the use of the highly toxic cyanogen chloride[ In an attempt to
overcome this problem it has been found that the reaction of cyanogen bromide "which is easier to
handle than cyanogen chloride# with the alkynyl cuprate "070# in diethyl ether:acetonitrile at 24>C
produces phenylpropynenitrile in 59) yield "Equation "35## ð65S337Ł[ Lower temperatures result in
poorer yields of the desired a\b!alkynic nitriles ð65S337Ł[ In a further modi_cation of this general
route into a\b!alkynyl nitriles\ phenyl cyanate "071# "prepared by the reaction of phenol with
cyanogen bromide in the presence of triethylamine# reacts with lithiated alkynides at −69>C in
diethyl ether to give a\b!alkynic nitriles "Equation "36## ð79S049Ł[ The reaction is quite general with
alkyl\ cycloakyl\ aryl and alkoxy substituted lithiated alkynides all providing the corresponding a\b!
alkynic nitriles in excellent yield "69Ð84)#[
BrCN
Cu CN (46)
(181)
R Li + Ph–O–CN R CN (47)
(182)
Metallated alkynides can also react with p!toluenesulphonyl cyanide "TsCN# leading to
a\b!alkynic nitriles ð82TL3512Ł[ In this case alkynic organozinc iodides are found to react smoothly
with TsCN in THF under very mild conditions "9Ð14>C\ 1 h# to give the desired alkynic nitriles in
excellent yield "70Ð89)# "Equation "37## ð82TL3512Ł[
565 a\b!Unsaturated and Aryl Nitriles
THF, 0 °C to 25 °C
R ZnI + TsCN R CN (48)
R = alkyl
The utility of a\b!alkynic nitriles in organic synthesis has been aptly demonstrated by the synthesis
of bongkrekic acid "072# ð73JA351Ł via the alkynic nitrile "075#[ The nitrile "075# was itself prepared
in a novel two!step procedure starting with the a!cyanoketone "073# "Scheme 50#[ Thus\ exposure
of the cyanoketone "073# to sodium hydride and then tri~ic anhydride _rst led to the enol tri~ate
"074#[ Elimination of the elements of tri~ic acid from "074# with sodium hydride in diethyl ether
and dimethyl sulfoxide next gave the a\b!alkynic nitrile "075# in a 54) yield from the cyanoketone
"073# ð73JA351Ł[ Reaction of "075# with dimethylcopper lithium then gave the Z!a\b!alkenic nitrile
"075# which was _nally elaborated to the bromoalkyne "077#\ the immediate precursor to bongkrekic
acid "072#[
CO2H
CO2H
OMe
CO2H
(183)
OMe OMe
NaH, Tf2O NaH, Et2O, DMSO
CN CN
TIPS O TIPS OTf
(184) (185)
OMe OMe CN
Me2CuLi steps
TIPS CN TIPS
(186) (187)
CO2Me
OMe
Br
(188)
Scheme 61
Copyright # 1995, Elsevier Ltd. All R ights Reserved Comprehensive Organic Functional Group Transformations
3.20
N-Substituted Nitriles and Other
Heteroanalogues of Nitriles of the
Type RCZ
R. MICHAEL PATON
University of Edinburgh, UK
2[19[0 N!SUBSTITUTED NITRILES 566
2[19[0[0 General Methods for the Formation of Nitrilium Betaines 566
2[19[0[1 Nitrile Ylides 567
2[19[0[2 Nitrile Imides 579
2[19[0[2[0 Generation of transient nitrile imides 579
2[19[0[2[1 Preparation of stable nitrile imides 570
2[19[0[3 Nitrile Oxides 572
2[19[0[3[0 From aldoximes 572
2[19[0[3[1 From nitromethyl compounds 573
2[19[0[3[2 From a!nitroalkanoate esters 573
2[19[0[3[3 From furazan N!oxides 574
2[19[0[3[4 Generation of fulminic acid and heteroatom!substituted analo`ues 574
2[19[0[4 Nitrile Sul_des 575
2[19[0[5 Nitrilium Ions 576
2[19[1 N!SUBSTITUTED ANALOGUES OF NITRILES BEARING A HETEROATOM
OTHER THAN NITROGEN 576
2[19[1[0 Phosphaalkyne Synthesis 576
2[19[1[1 Methods for the Synthesis of AlkylidyneÐTransition Metal Compounds 589
2[19[1[1[0 Synthesis from nonalkylidyne precursors 589
2[19[1[1[1 Modi_cations of alkylidyneÐmetal complexes 580
566
567 Nitriles and Other Heteroanalo`ues of Nitriles
has not yet been exploited synthetically and they are therefore omitted from the survey[ Methods
for the formation of nitrilium ions "RC2N¦R# are considered in the _nal section[ The generation
and reactions of the nitrilium betaines and mechanistic aspects of their chemistry have been described
in depth as part of wider reviews ð80COS"3#0958\ 80COS"3#0000Ł\ and also in a two!volume monograph
on 0\2!dipolar cycloaddition chemistry edited by Padwa ðB!73MI 219!90Ł[ Reference to reviews speci_c
for the individual classes of nitrilium betaine is made in the appropriate sections of this chapter[
R Y R Y
X Y + R X Y
X R N Z– + X
N –
N Z N
Z Z
Scheme 1
As most nitrilium betaines usually exist at ambient temperature only as short!lived intermediates\
it is common practice in synthetic applications for them to be generated in situ in the presence of
the dipolarophile[ In this way\ side reactions which compete with cycloaddition are minimised[ No
single method is applicable for the generation of all four classes of nitrilium betaine[ There are\
however\ two approaches which are common to more than one type and are widely used[ These are
outlined in the following paragraphs[
The most widely used route "Equation "0## involves the dehydrohalogenation of the appropriately
substituted imino compounds "RCX1NZH#[ Thus nitrile ylides\ nitrile imides and nitrile oxides
can be conveniently formed from imidoyl halides "RCX1N0CHR1#\ hydrazonoyl halides
"RCX1N0NHR# and hydroximoyl halides "RCX1N0OH#\ respectively[ The elimination of HX
is usually carried out by treatment with base but can sometimes be accomplished by thermolysis
alone[
The second generally applicable approach involves thermally or photochemically induced frag!
mentation "with expulsion of a stable moiety such as carbon dioxide or nitrogen# of a _ve!membered
heterocyclic compound which already incorporates the C1N0Z moiety "Equation "1##
ð68AG"E#610Ł[ This is the method of choice for nitrile sul_des and is also widely used for nitrile ylides
and nitrile imides[
R Y heat or hν +
X R N Z– (2)
N Z –X = Y
situ generation of arenenitrile ylides[ The precursors are easily prepared from N!monoalkylated
carboxamides by treatment with SOCl1\ PCl4 or COCl1 and\ provided the proton at the alkyl group
attached to nitrogen is su.ciently acidic\ formation of the nitrile ylide is readily induced by addition
of a base such as triethylamine[ The process is faster in the presence of a dipolarophile and is
believed to involve an equilibrium between imidoyl halide and HCl:nitrile ylide\ the latter being
present only at low concentration[ It has been reported ð61CB0147Ł that triethylamine hydrochloride
also causes tautomerism between the regioisomeric imidoyl chlorides Ar0CCl1NCH1Ar1 and
Ar0CCH1N1CClAr1\ thus leading to the generation of both nitrile ylide isomers
Ar0C2N¦0C−HAr1 and Ar0CH−0N¦2CAr1[
R
R X
R R
Y
N N
X heat or hν R
base R
–HX –X Y (3) X = O, Y = CO
+
R (4) X = CO, Y = O
– (5) X = O, Y = PR3
R N R
: (6) X = S, Y = PR3
R
hν R
N
R
R N
R
R
Scheme 3
1H!Azirenes undergo photochemical\ but not thermal\ ring opening at C"1#0C"2# to a}ord nitrile
ylides "Scheme 2# and\ as there are e.cient methods available for the synthesis of such azirenes
bearing a wide range of substituents\ this is a valuable strategy for the generation of this class of
0\2!dipole ð73JOC2063Ł[ It is\ for instance\ suitable for low!temperature spectroscopic studies[ The
process can be reversible\ and with light of longer wavelength "249 nm#\ benzonitrile ylides are
transformed back into 2!phenyl!1H!azirenes[ Benzonitrile ylides are also formed on photolysis of
0!azido!0!phenylalkenes\ presumably via the 1H!azirene as intermediate ð63HCA0271Ł[ The photo!
chemistry of nitrile ylides has been reviewed ð65ACR260\ B!71MI 219!90Ł[
Additions of a singlet carbene or carbenoid to a nitrile represent an elegant alternative method
for nitrile ylide generation ð80CRV152Ł[ The reactions are particularly useful for alkyl! and acyl!
substituted nitrile ylides for which some of the traditional methods are unsuccessful[ For example\
singlet methylene\ generated by photolysis of either diazomethane or diazirene\ combines with
acetonitrile to a}ord acetonitrile methanide "CH2C2N¦0CH1−# ð75JA5628Ł[ Rhodium acetate!
mediated fragmentation of a!diazoketones and acetates in the presence of nitriles leads to C!acyl
and C!alkoxycarbonyl analogues ð81CL1086Ł[ The _rst stable nitrile ylide "1# was prepared by this
approach in 0873^ its unusual stability is attributed both to the steric bulk of the C!adamantyl
substituent inhibiting dimerisation and to charge delocalisation at the N!terminus into the cyclo!
pentadienyl ring ð73TL394Ł[
CF3
F3C
– +
N
F3C
CF3
(2)
579 Nitriles and Other Heteroanalo`ues of Nitriles
Nitrile ylides are formed on thermal or photochemically!induced fragmentation of several hetero!
cyclic systems "Scheme 2#[ Carbon dioxide is expelled on photolysis or thermolysis of 1! and
2!oxazolin!4!ones "2# and "3#\ which are readily prepared bearing a variety of substituents starting
from amino acids[ The temperature required "099Ð129>C# depends on the nature of the substituents
ð60CB2705\ 77HCA0066Ł\ 2!oxazolin!4!ones generally fragmenting more readily than their 1!oxazo!
linone isomers[ Similarly 1\2!dihydro!0\3\1l4!oxazaphospholes "4# and !thiazaphospholes "5# ther!
mally or photochemically extrude triakyl phosphate and thiophosphate respectively ð79CB1588\
75AG"E#74Ł[ 1\1!Bis"tri~uoromethyl#!2!oxazolin!4!one:P"OMe#2 acts as a synthon for formonitrile
hexa~uoro!1!propanide ð76S813Ł[ Benzonitrile bis"tri~uoromethyl#methanide is formed together
with phenyl isocyanide on ð2¦0Ł cycloreversion of azetidinimine "6# ð62AG"E#044Ł[
Ph NPh Ph N R TMS
NCO2Et N
N CF3 HN
PhS
CF3
(7) (8) (9)
N R2
+ –
hν
R1 N NR2 N N • N
R1 R2
R1
hν
R2 R2
N N R1 N N
R1
N2 R1 R1
R2 R2 N N
R1 N N
R2
(10) (11)
Scheme 4
and by thermal decomposition of 1\4!diphenyltetrazole\ and these remain two of the most used
approaches to this class of nitrilium betaine[
Hydrazonoyl chlorides are readily prepared by a variety of methods including treatment of
hydrazides with PCl4 ðB!68MI 219!90Ł\ Ph2P:CCl3 ð76JHC466Ł or POCl2:pyridine ð65ZOR0565Ł and
by chlorination of aldehyde hydrazones ð61RCR384Ł^ use of Ph2P:CBr3 provides access to the
corresponding bromides ð64CJC0222Ł[ Coupling of diazonium salts with halogenated methylene
compounds and with diazo compounds can be used for the preparation of C!acyl and C!alkoxy!
carbonyl analogues ð48OR"09#032Ł[ Addition of a base such as triethylamine a}ords the nitrile imide
by a pathway which is believed to involve initial removal of the NH proton followed by loss of
halide ion ð61JCS"P1#33Ł[ Base!induced elimination of nitrous acid from a!nitro aldehyde hydrazones
has also been investigated "Scheme 4#\ and in some cases hydrazones can be oxidised to nitrile
imides directly\ for example with lead tetraacetate ð57CI"L#326\ 58JCS"C#1476Ł[
R1
NNHR2 R1 N
X N
X = Cl, Br, NO2 N N
base heat or hν R2
–HX –N2 (12)
+ –
R1 N NR2
heat or hν hν
–XO2 –CO2
hν –CO2 –O
R1 O O
R1 + N
X O N R1
N N O N
N R2
R2 R2
(14) X = C O (13)
(16) X = S (15)
Scheme 5
Tetrazoles "01# provide another valuable source of nitrile imides[ They are accessible by several
routes including oxidation of formazans\ treatment of aldehyde hydrazones with aryl azides and
diazotisation of amidrazones ð73CHEC"4#680Ł[ Photolysis\ or thermolysis in an inert solvent results
in extrusion of nitrogen^ the temperature required ranges from 059 to 119>C depending on the
electron donatingÐwithdrawing properties of the imide substituent[ The ~ash vacuum pyrolysis
technique coupled with low!temperature matrix isolation has also been used ð74AG"E#45Ł[ Thermal
or photochemically!induced fragmentation of various other diazoles a}ords nitrile imide derived
products ð68AG"E#610\ B!73MI 219!92Ł] for example\ the decarboxylation of the mesoionic compound
"02# and the oxadiazolinones "03# and "04#\ and extrusion of sulfur dioxide from the oxathiadiazole
"05#[
The original route employing diazolithium precursors has proved to be general and a wide range
of stable nitrile imides have been similarly prepared by combination of chlorosilanes\ chloroboranes
and chlorophosphanes with the lithium salts of phosphino!\ boryl! and silyl! as well as thiophos!
phinoyl!diazomethanes[ Electrophilic attack can occur at carbon yielding a substituted diazo com!
pound\ or at nitrogen to form the nitrile imide ð81JA5948Ł[ The balance between the two processes
has been shown to depend on steric factors\ bulky electrophiles reacting preferentially at nitrogen
and less sterically demanding analogues at carbon[ Diazo compounds can also result from iso!
merisation of the thermodynamically less stable nitrile imide "Scheme 5#[
+ –
N - attack R N NE
R
N2 + E+
Li R
C - attack
N2
E
Scheme 6
Me3Sn
+ –
N2 + RCl R N NR (4)
Me3Sn
(18) (19) R = B(NPri2)2
(20) R = P(NPri2)2
(21) R = CPh3
Some chemical modi_cations have also been performed on carbon and nitrogen substituents
without destroying the CNN skeleton^ for example\ a C!phosphino group can be converted into the
corresponding C!thiophosphinoyl by treatment with elemental sulfur ð80OM2194Ł[ An alternative
approach to stable nitrile imides involves replacement of boryl groups at both carbon and nitrogen
termini ð81S32Ł[ Reaction of the bis"diisopropylamino#boryl compound "11# with methyllithium
followed by a chlorophosphane a}ords the C!phosphino derivative "12# "Scheme 6#\ and the diboryl!
substituted analogue "13# is formed by a similar two!step sequence[
i, MeLi i, MeLi
+ ii, R12PCl +
ii, R22BCl +
– – –
R12P N NBR12 R12B N NBR12 R22B N NBR22
iii, MeLi
(23) (22) iv, R22BCl (24)
R1 = PriN, R2 = (c-C6H11)2N
Scheme 7
The stable organometallic nitrile imides described above are of interest in their own right and
have allowed the structure\ bonding and properties of the CNN framework to be examined in detail[
In some cases they also provide further scope\ as yet not fully realised\ for the synthesis of heterocyclic
Substituted Nitriles 572
compounds via the reactions of their substituents[ Whereas phosphorusÐcarbon bonds in the
cycloadducts are not readily cleaved\ the corresponding boronÐcarbon and siliconÐcarbon bonds
are more susceptible to substitution[ C!Silyl and C!boryl nitrile imides may therefore provide useful
building blocks for the preparation of _ve!membered heterocycles incorporating the C1N0N unit[
R
RN • O R R NOH
Nu
+
N N
O O–
(25)
Scheme 8
X+ –HX
base
R or heat
NOH
X
Scheme 9
As some hydroximoyl halides are di.cult to isolate in pure form and others are toxic\ for example\
as skin irritants\ it is common practice to generate them in situ using NCS or NBS\ and then to carry
out the dehydrochlorination:cycloaddition in one pot using triethylamine as the base[ Treatment of
aldoximes with t!butyl hypochlorite followed by bis"tributyltin# oxide also a}ords nitrile oxides\
presumably via the O!stannyl oxime "RCH1NOSnBu2# ð83JCS"P0#302Ł[ Other reagents which allow
one!pot halogenation:dehydrohalogenation include sodium hypochlorite ð71S4497Ł\ sodium hypo!
bromite ð56JOC1292Ł and Chloramine!T ð78S46Ł[ Oxidations of aldoximes to nitrile oxides have also
been accomplished using lead tetraacetate ð57T4140Ł\ mercuric acetate ð81OPP80Ł and dimethyl!
dioxirane ð81NKK319Ł[
O
EtO2C EtO2C O
EtO2C –EtOH –CO2 +
NO2 OEt EtO2C N O–
+N O
EtO2C N+ –O
–O OH
(27)
Scheme 11
(CH2)n
–O + + O–
heat
N N (5)
+ ( )n
N N
O O–
Two other preparatively useful approaches to nitrile sul_des have been reported[ Heating "ben!
zylimino#sulfur di~uoride\ prepared from benzylamine and SF3\ with sodium ~uoride and 07!crown!
5!polyether at 029>C generates benzonitrile sul_de which can be trapped by reactive dipolarophiles
such as dimethyl acetylenedicarboxylate ð68JOC409Ł[ The reaction is believed to involve 0\2!elim!
ination of two moles of HF\ as illustrated in Scheme 03^ acetonitrile sul_de and tri~uoroacetonitrile
sul_de have also been generated by this route ð79JOC2642Ł[
Ar F Ar Ar +
:
N S N S F N S
H F H
+
F– F– Ar N S–
S S– S
–Ph2S
N N N
+
Ar SPh2 Ar SPh2 Ar
(31)
Scheme 14
Nitriles Bearin` a Heteroatom Other Than Nitro`en 576
Thermolysis "49Ð69>C# of N!thioaroyl diphenylsul_mides\ which can be synthesised from diphenyl
sul_mide and methyl dithiobenzoates\ in the absence of a dipolarophile a}ords the corresponding
nitriles together with diphenyl sul_de and sulfur[ However\ when the reaction is repeated in the
presence of electron!poor alkynes isothiazoles are formed ð65BCJ2013Ł\ presumably via the unstable
antiaromatic thiazirine "20# and the arenenitrile sul_de as intermediates "Scheme 03#[
Benzonitrile sul_de has been invoked as a transient intermediate in the photofragmentation
reactions of various phenyl!substituted _ve!membered heterocycles incorporating C\ N and S[ In
each case the process is believed to involve extrusion of a stable fragment such as CO1\ COS\
CS1\ N1 or N1O forming the thiazirene "20#\ followed by rearrangement to benzonitrile sul_de[
Representative examples include dithiazolethiones "21# and "22#\ thiatriazole "23# and mesoionic
oxathiazolone "24# ð67JCS"P0#0334\ 70LA0914Ł[ Although the intermediates have been detected
spectroscopically\ the yields of cycloadducts in the presence of a dipolarophile are generally low
"4Ð18)#[
O–
Ph S Ph N Ph Ph
N
S S N + O
N S S S S N S N
Some phosphaalkynes with heteroatom substituents attached to carbon are included here for convenience[ See also 2[19 and
4[22[
577 Nitriles and Other Heteroanalo`ues of Nitriles
R1 R2 +
–C N R2
N
X
(37)
–X– R1X
+
R1 N R2
(36) SbCl5
R2X
–CO2 R1 OCOX
R1 N N
R2
(38)
Scheme 15
of the series\ the unstable and highly reactive methylidynephosphane "phosphaacetylene\ HC2P#\
was characterised in 0850 ð50JA0658Ł it was not until 0870 that the preparation of a kinetically stable
analogue "tert!butylphosphaalkyne\ ButC2P# was _rst reported ð70ZN"B#05Ł[ Since this time a rich
and varied chemistry has emerged[ Despite in many cases substantial steric hindrance\ they undergo
a wide range of reactions including ð1¦0Ł!cycloadditions\ ð0\2Ł!dipolar cycloadditions and DielsÐ
Alder reactions^ ð1¦1Ł!cycloadditions\ HOMO!DielsÐAlder additions and ene reactions involving
C2P have also been described[ The synthesis and reactions of phosphaalkynes has been the
subject of several reviews by Regitz ð77AG"E#0373\ 89CRV080\ 81BSB248\ 83JHC552Ł\ and their impact on
organometallic chemistry has also been surveyed by Nixon ð77CRV0216\ 82CI"L#393Ł[
b!Elimination from suitably substituted phosphanes is the most generally applicable approach to
phosphaalkynes "Scheme 05#[ Flash pyrolysis of the dichlorophosphane "28# results in extrusion of
HCl which is removed by added base to avoid side and retro!reactions[ This method is suitable for
the generation of the short!lived parent phosphaacetylene and derivatives including RC2P\ where
RH\ Me\ F\ Cl[ Analogues with conjugating substituents such as HC2C0 and N2CC2
C0 are formed on co!pyrolysis of phosphorus trichloride with the propargyl halide[ The phosphino!
substituted compound "Me1N#2P¦0C2P[Ph3B− has been prepared by base!induced dehydro!
chlorination of the corresponding dichlorophosphane ð80CC291Ł[ Various transient phosphaalkynes
can be generated by dehydrochlorination of a\a!dichlorophosphanes "39# ð80AG"E#085Ł[ Flash vac!
uum pyrolysis "FVP#!induced b!elimination of trimethylsilyl chloride from chlorophosphaalkene
"30# proceeds similarly and has been used to form the phenyl and trimethylsilyl compounds[ Lithium
trimethylsilanoate is readily eliminated from the lithiated alkenes RC"OTMS#1PLi[
TMS
R PCl2 PCl
R
(39) heat heat (41)
–2 HCl –TMS-Cl
R P
K2CO3
heat heat
Cl TMS-O
–2 HCl –TMS-O-TMS
R PH2 P-TMS
Cl R
(40) (42)
Scheme 16
The most well!developed method for the synthesis of kinetically stable phosphaalkynes involves
NaOH!catalysed elimination of hexamethyldisiloxane from phosphaalkenes "31#[ The starting
materials can be prepared by acylation of tris"trimethylsilyl#phosphane\ a process which is believed
to involve initial formation of the acylphosphane RCOP"TMS#1 followed by a rapid 0\2!shift of a
trimethylsilyl group[
The 0 ] 0 adduct "32# between tris"trimethylsilyl#phosphane and isopropyl isocyanate provides a
source of the donor!substituted phosphaalkyne "33# ð78AG"E#42Ł which then undergoes NaOH!
catalysed elimination of hexamethyldisiloxane\ the _nal product being formed "Scheme 06# by a
0\2!silyl shift in the intermediate 0!aza!2!phosphaallene "34#[ The corresponding tert!butyl precursor
Nitriles Bearin` a Heteroatom Other Than Nitro`en 578
"35# reacts similarly and\ with replacement of the TMS group by hydrogen\ generates tert!
butylaminophosphaacetylene "ButNHC2P# ð80HAC466Ł[ The diisopropylamino compound
Pri1NC2P is prepared by the reaction of tri~uoromethylphosphane with excess diisopropylamine\
presumably via the phosphaalkene Pri1NCF1PH ð89CB1206Ł[
RN Pri
–TMS-O-TMS
P(TMS)2 PriN C P-TMS N P
TMS-O TMS
(43) R = Pri (45) (44)
(46) R = But
Scheme 17
R
–N2 – CH2=CMe2
:
:
N2 RC PBut R PBut2 R P
PBut
(47)
Scheme 18
Li R
–LiCl R – +
P C P R R P
:C P
Cl
Scheme 19
The generation of stabilised quinquevalent "l4s2# phosphaalkynes has been the subject of inves!
tigation since the late 0879s[ These compounds show an interesting pattern of reactivity and can act
both as a phosphaalkyne "RC2PR1# in addition and cycloaddition reactions\ and as a nucleophilic
phosphanylcarbene "RC0PR1# capable of C0H insertion[ Two examples have been studied in
particular detail[ Bertrand and co!workers have shown that the trimethylsilyl derivative "37# bearing
diisopropylamino!stabilising substituents can be generated by photolysis of phosphiniodiazo com!
pound "38#\ which is readily prepared from the chlorophosphine and the lithiated diazo compound
"49# "Scheme 19# ð77JA5352\ 89PS"38#290Ł[ Under FVP conditions the product can be isolated[ A
similar procedure has been adopted by Regitz and co!workers to form phosphino analogue "40#
starting from the silver diazo compound "41# ð75TL0892Ł[ A few isolated examples of the related
l5s3!thiaalkynes have also been described ð74JA879\ 77AG"E#0423Ł^ the methylidynesulfur tri~uoride
derivatives RC2SF2 "RCF2\ SF2# were prepared by KOH!induced dehydro~uorination of
CF2CH1SF4 "or CF2CH1SF3# and SF2CH1SF4\ respectively[
Arsaalkynes have so far received much less attention[ Following the technique successfully
R R heat or hν
N2 + (Pri2N)2PCl N2 R P(NPri2)2
P(NPri2)2 –N2
X
(50) R = TMS, X = Li (49) R = TMS (48) R = TMS
(52) R = Ph2P(O), X = Ag (51) R = Ph2P(O)
Scheme 20
589 Nitriles and Other Heteroanalo`ues of Nitriles
developed for phosphaalkynes the kinetically stabilised l2s0!derivatives of the form RC2As\ where
RBut and 1\3\5!But2C5H1\ have been generated by ~uoride!ion induced elimination of hexa!
methyldisiloxane from the arsaalkene RC"OTMS#1AsTMS ð75AG"E#153\ 82AG"E#092Ł[
Abstraction with base of an a!hydrogen atom from a carbene ligand LnM1CHR has been
utilised for the preparation of various anionic carbyne complexes ðLnM2CRŁ−^ the conversion of
a neopentylidene into a neopentylidyne ligand involving abstraction of a proton by butyllithium is
illustrated by the formation of ð"CH1But#2Ta2CButŁLi"dmp#1 from "CH1But#2Ta1CHBut in the
presence of N\N?!dimethylpiperazine "dmp#[ Removal of two a!protons from "h4!C4Me4#
"CH1But#ReO using Ti"h4!C4H4#Cl2 a}ords the Re"VI# complex Cl1"h4!C4Me4#Re2CBut[ Depro!
tonation of h1!carbene complexes can also lead to carbynes[ Migration of an a!hydrogen promoted
by the addition of phosphines has also been observed^ trimethylphosphine with Cl"Cp#"CH1But#
Nitriles Bearin` a Heteroatom Other Than Nitro`en 580
Ta1CHBut a}ords Cl"Cp#"PMe2#1Ta2CBut and Cl"Cp#"CH1Ph#2Ta yields the corresponding
benzylidyne complex\ presumably via a carbene intermediate[ Alkenyl ligands in LnM0CR1CR1
are capable of rearrangement into carbynes LnM2CR2^ for example\ an H!shift in molybdenum\
the complex CpðP"OMe#2Ł2Mo0CH1CHBut leads to CpðP"OMe#2Ł2Mo2CCH1But[
The formal abstraction of oxide\ O1−\ from acyl or carbamoyl ligands is another direct route to
carbyne complexes[ The approach is illustrated by the formation of the alkylidyne"halo#tetra!
carbonyl complexes\ trans!X"CO#3M2CR where MCr\ Mo and W\ from the reaction of oxaloyl
halides with the anionic pentacarbonylmetal acyl complexes NMe3ð"CO#4MCORŁ[ The amino!
carbyne complex trans!Cl"CO#3W2CNEt1 is formed similarly by treatment of Lið"CO#4WCORŁ
with thionyl chloride[
b!Addition\ particularly of electrophiles\ to unsaturated ligands is another general approach
to carbynes "Scheme 10#[ Protonation of acetylide and alkylidene has proved useful for the
synthesis of high oxidation state molybdenumÐalkylidyne complexes^ for example\ Br"Cp#ðP
"OMe#2Ł1Mo1C1CHPh is converted into Br"Cp#ðP"OMe#2Ł1Mo2CCH1Ph in the presence of
HBF3\ and the manganese complex ðCp"CO#1Mn2CCPh1ŁBF3 is formed similarly from
Cp"CO#1Mn1C1CPh1[ b!Addition of hydride to alkylidene ligands is also possible[ Other ligands
which have been successfully converted into carbynes by b!addition of electrophiles include isocy!
anide\ carbonyl and thiocarbonyl "Scheme 10#[
E E
E+ E+
LnM R LnM • LnM R
R E
E
+ R E+
L nM N R LnM N
LnM • N
R
E+
LnM • X LnM X E
X = O, S
Scheme 21
(ButO)3W W(OBut)3
(53)
R N (ButO)3W R + (ButO)3W N
(54)
Scheme 22
Several novel alkylidyne complexes have been synthesised by modi_cation of the substituent
attached to the carbyne carbon[ This can involve manipulations within the group or its complete
replacement[ Examples in the former category include the addition of dimethylamine to ethynyl!
carbyne ditungsten compounds L"CO#3W2C0C2CPh yielding L"CO#3W2C0CH1C
"NMe1#Ph\ and desilylation of LðP"OMe#2Ł1Mo2CCH1TMS by NaF:aq[ MeCN to form LðP
"OMe#2Ł1Mo2CCH2[ Nucleophiles can displace leaving groups such as chloride from the carbyne^
for example\ treatment of trans!L"CO#1Mo2CCl with phenyllithium a}ords the benzylidyne deriva!
tive L"CO#1MoC2CPh[
Metal alkylidyne complexes undergo various oxidation and reduction reactions[ Thus\ bromine
oxidation of trans!Br"CO#3M2CR "MMo\ W^ RMe\ Ph\ CH1But# in the presence of 0\1!
dimethoxyethane "DME# a}ords the DME!stabilised complexes Br2"DME#M2CR and represents
conversion of a Fischer!type into a Schrock!type complex ð75JA437Ł[ Reductions of these products
"Zn:MeCN:PMe2# then provide access to carbonyl!free Fischer complexes of the form
Br"PMe2#3M2CR[
Copyright # 1995, Elsevier Ltd. All R ights Reserved Comprehensive Organic Functional Group Transformations
3.21
Isocyanides and their
Heteroanalogues (RZC)
IAN A. O’NEIL
University of Liverpool, UK
2[10[0 ISOCYANIDES 582
2[10[0[0 General Methods for Isocyanide Synthesis 582
2[10[0[0[0 The alkylation and alkynation of cyanides 583
2[10[0[0[1 The reaction of primary amines with dichlorocarbene "the Hofmann carbylamine reaction# 584
2[10[0[0[2 a!Eliminations from formic acid derivatives of primary amines 584
2[10[0[0[3 Deprotonation and further elaboration of isocyanides 586
2[10[0[0[4 Use of or`anometallic isocyanides 587
2[10[0[0[5 Reduction of isocyanates\ isothiocyanates and isocyanide dihalides 587
2[10[0[0[6 Miscellanous methods 588
2[10[0[1 Aliphatic Isocyanide Synthesis 588
2[10[0[1[0 Saturated isocyanide synthesis 588
2[10[0[1[1 b and more remotely unsaturated isocyanides 699
2[10[0[1[2 Halo!substituted isocyanides 691
2[10[0[1[3 Aliphatic isocyanides bearin` an oxy`en!based functional `roup 692
2[10[0[1[4 Aliphatic isocyanides bearin` a sulfur!based functional `roup 697
2[10[0[1[5 Aliphatic isocyanides bearin` a Se! or Te!based functional `roup 698
2[10[0[1[6 Aliphatic isocyanides bearin` a nitro`en!based functional `roup 698
2[10[0[1[7 Aliphatic isocyanides bearin` other substituents 600
2[10[0[2 a\b!Unsaturated Isocyanides 601
2[10[0[2[0 General methods 601
2[10[0[2[1 Isocyanides bearin` an a\b!double bond 604
2[10[0[2[2 Isocyanides bearin` an a\b!aryl or hetaryl substituent 610
2[10[1 ISOCYANIDE ANALOGUES WITH A HETEROATOM OTHER THAN NITROGEN 615
2[10[0 ISOCYANIDES
The _rst isocyanide was prepared accidently by Lieke in 0748 when he treated allyl iodide with
silver cyanide in an attempt to prepare allyl cyanide ð0748LA"001#205Ł[ The product he obtained had
a {{penetrating and vile odor^|| indeed\ the odor was so unpleasant that many of his subsequent
experiments were performed outdoors[ Several years later\ Meyer reported the preparation of methyl
and ethyl isocyanide by the alkylation of silver cyanide ð0755JPR036Ł[ In 0756\ Hofmann described
the synthesis of isocyanides from primary amines by treating them with KOH and chloroform
ð0756LA"033#003Ł[ This synthesis subsequently became known as the Hofmann carbylamine reaction\
and was used for many years as a diagnostic test for primary amines[ The _rst truly general synthesis
of isocyanides\ the dehydration of N!monosubstituted formamides\ was developed in the 0859s[ The
582
583 Isocyanides and their Heteroanalo`ues
pioneering work of Ugi in this area led to the introduction of phosgene as the reagent of choice for
this transformation ð54AG"E#361Ł[ These developments allowed the general synthetic applications of
isocyanides to be explored[
In the nineteenth century\ the structure of isocyanides presented something of a dilemma[ Gautier
saw isocyanides as {{true homologs of hydrocyanic acid\|| since like the acid\ {{they have the greatest
deleterious e}ect on an organism[|| On the basis of his hydrolysis results\ Gautier proposed the _rst
structural formula for ethyl isocyanide "0# ð0758LA"035#008Ł[ He later went on to suggest structures
"1# and "2#[ Some years later\ Nef proposed structure "3# because of the large number of a!addition
reactions of the isocyanide carbon ð0781LA"169#156Ł[ In 0829\ a polar structure "4# was proposed by
Lindemann and Wiegrebe in analogy with the structure of carbon monoxide ð29CB0549Ł[
C
N + –
C2H5
Et N C Et N C Et N • R N C
(1) (2) (3) (4) (5)
Hammick found the partial dipole moment of the isocyano group to be opposite to that of the
cyano group ð29JCS0765Ł[ Shortly after\ Brockway ð25JA1405Ł and then Gordy and Pauling
ð31JA1841Ł\ presented electron di}raction data which supported a predominantly triple!bonded
structure[ The infrared data of isocyanides indicated an almost triple!bonded structure\ although
this did not rule out a double!bond structure entirely[ Finally\ two decades after the proposal of
Lindemann and Wiegrebe\ extensive microwave studies provided perhaps the most conclusive
evidence for structure "4# ð49MI 210!90Ł[ These results proved the linearity of the C0N0C bond
system beyond doubt[
The almost unique property of isocyanides in bearing a formally divalent carbon allows them to
engage in a range of unique reactions\ and they are endowed with a rich and versatile chemistry[
a!Addition reactions are particularly common\ and this has been exploited in the elegant work of
Passerini and Ugi ð80COS"3#0972Ł[ Ugi has shown that isocyanides participate in four!component
condensations "3CC# and this work has been extended to _ve! ð50CB1791\ 67M638Ł and even seven!
component condensations ð82AG"E#452Ł[ Schollkopf pioneered the use of a!metallated isocyanides
in synthesis ð66AG"E#228\ 68PAC0236Ł\ and the tosylmethyl isocyanide "TosMIC# reagent of van
Leusen has found widespread use in the synthetic community ð61SC170\ 63LA33\ 66TL3118\ 79S214\
74RTC49\ B!76MI 210!90\ 81S30\ 81TA176Ł[ Ito has contributed extensively to the synthetic chemistry of
isocyanides ð77JOC3047\ 77PAC472\ 89JA1326Ł[ Isocyanides have also found use in the synthesis of
novel polymers ð61CRV0909\ 81AG"E#0498\ 82JA8090Ł[ Finally\ the recent terrestrial synthesis of ethynyl
isocyanide ð80AG"E#0533Ł\ and its subsequent detection in interstellar space\ has implications for the
role of isocyanides in prebiotic chemistry ð60T2958Ł[
Until relatively recently\ very few naturally occurring isocyanides were known^ however\ there
are currently more than 199 isocyanide containing natural products[ This area has been reviewed
recently ð77MI 210!90\ 78PAC498\ 81ACR322Ł[ This review does not cover the extensive coordination
chemistry which isocyanides participate in ð79CCR082\ 72AOC"11#198\ 83AG"E#0204Ł\ but deals with the
synthetic organic methods for their preparation[ The chemistry of isocyanides was last reviewed
comprehensively by Ugi ðB!60MI 210!90Ł\ and several more general reviews of isocyanide chemistry
have been published ðB!72MI 210!90\ 74HOU"E4#500Ł[ Subsequent to this\ several updated and more
specialized reviews on isocyanides have been published[ These include the Ugi and Passerini
reactions ð71AG"E#709\ 80COS"3#0972Ł\ ~uorinated isocyanides ð83AG"E#0204Ł\ functionalized iso!
cyanide metal complexes ð82CRV0132Ł\ and multidentate isocyanides ð82AG"E#549Ł[
In this introductory section\ the various general methods for the synthesis of isocyanides are
discussed[ More speci_c examples are given in the appropriate section[
There are seven methods for isocyanide synthesis^ these are shown below]
"i# the alkylation and alkynation of cyanides\
"ii# the reaction of primary amines with dichlorocarbene "the Hofmann carbylamine reaction#\
"iii# a!eliminations from formic acid derivatives of primary amines\
"iv# deprotonation and further elaboration of isocyanides\
"v# use of organometallic isocyanides\
"vi# reduction of isocyanates\ isothiocyanates and isocyanide dihalides\ and
"vii# miscellaneous methods[
2[10[0[0[0 The alkylation and alkynation of cyanides
The treatment of alkyl iodides with silver cyanide was the _rst preparative procedure for the
synthesis of isocyanides[ Treatment of ethyl iodide with silver cyanide yields the silver complex of
Isocyanides 584
ethyl isocyanide[ This is not routinely isolated\ but treated with potassium cyanide to liberate the
free isocyanide "Scheme 0# ð52OSC"3#327\ 68TL052Ł[ The mechanism of this reaction has been studied
in some detail ð74TL2270Ł[ In general\ the yields are modest and the use of expensive silver salts
limits the scale on which this reaction can be performed[
KCN
EtI + AgCN EtNC•AgI Et NC
Scheme 1
Songstad and co!workers have reported improved yields by the use of onium dicyanoargenates
in the preparation of di! and triphenyl isocyanides ð63ACS"A#144Ł[ Silver cyanide has also been used
in the synthesis of more highly functionalized isocyanides[ For example\ treatment of the glycosyl
bromide of 1!deoxy tri!O!benzyl!D!glucose gives the anomeric isocyanide in 79) as a single "a#
anomer "Equation "0## ð65TL2316Ł[
OBn OBn
O AgCN, 15 min O
BnO BnO (1)
BnO BnO
Br NC
Alkyl isocyanides can also be obtained by treating the alkylation products of silver hexa!
cyanoferrates or hexacyanocobaltates with the hydroxides ð16M60Ł\ or cyanides ð17JCS679Ł of the
group 0 metals\ or even simply by heating ð48AG275Ł[ When ethanolic solutions of hydrogen
hexacyanoferrate and HCN are heated to 019>C\ up to 39) of ethyl isocyanide is formed
ð50JOC2115Ł[
2[10[0[0[1 The reaction of primary amines with dichlorocarbene "the Hofmann carbylamine reaction#
The carbylamine reaction\ _rst described by Hofmann\ was one of the earliest general methods
for isocyanide synthesis[ In its simplest form\ the reaction involves the treatment of a primary amine
and chloroform with an aqueous solution of KOH[ The reaction is thought to involve the generation
of dichlorocarbene\ its addition to the primary amine\ and a sequential b! and a!elimination
"Scheme 1#[
CHCl3, KOH – R
R + CCl2 proton transfer α-elimination
R NH2 N N R NC
[:CCl2] H2 β-elimination
Cl
Scheme 2
Several problems\ particularly with respect to yield were apparent in the earlier procedures[
Mainly due to the e}orts of Ugi ð61"AG"E#429Ł\ Weber ð61TL0526Ł and Gokel ð77OSC"5#121Ł who
introduced the use of phase transfer catalysts\ good yields of isocyanides can now be obtained using
this approach[ An interesting variation involves the use of aliphatic hydrazones as substrates[ On
treatment with chloroform:KOH under phase transfer conditions the isocyanoimines are isolated
ð65ACS"B#884Ł[ Mayer and co!workers have reported the conversion of N!sul_nylamines into iso!
cyanides by reaction with CHCl2 and solid KOH in the presence of a phase transfer catalyst ð66S164Ł[
Finally\ dichlorocarbene has been found to cleave carbodiimides to form isocyanides and isocyanide
dichlorides ð55TL078Ł[
A large number of di}erent reagents are available to e}ect this transformation[ Currently\ the
most widely used dehydrating reagents used are based on phosgene[ Ugi was the _rst to describe
the use of phosgene in the presence of a tertiary amine ð50CB1703Ł[ A number of tertiary amines
have been used\ including trimethylamine\ triethylamine\ tri!n!butylamine\ N\N!dimethyl!
cyclohexylamine\ N\N!dimethylaniline\ pyridine\ quinoline\ and 0\3!diazabicycloð1[1[1Łoctane
"dabco# ð54AG"E#361Ł[ The base of choice does appear to be triethylamine\ owing to a combination
of cost and volatility[ The high toxicity and handling properties associated with phosgene have led
to the use of diphosgene and triphosgene in the preparation of isocyanides[ Diphosgene "trichloro!
methyl chloroformate# ð69OS"49#084Ł is a stable liquid which has been reported to give higher yields
than phosgene in the dehydration of formamides to isocyanides ð66AG"E#148Ł[ More recently\
triphosgene "bis"trichloromethyl#carbonate# in the presence of a tertiary amine base has been used
to e}ect the dehydration ð76AG"E#783Ł[ Triphosgene has the advantage that it is a crystalline material
of low volatility\ which can be readily weighed out under anhydrous conditions[
The use of POCl2 in the presence of a tertiary amine has also found widespread use in the
dehydration of formamides to isocyanides[ The bases that have been used include pyridine
ð62OSC"4#299\ 78TL0704\ 89T5240Ł\ triethylamine ð77OSC"5#876\ 77OSC"5#519Ł\ 1\5!lutidine ð73TL4964\
77OSC"5#121Ł\ diisopropylamine ð74S399\ 75SC754\ 77LA654\ 89CB524Ł\ and potassium t!butoxide
ð75ZN"B#021Ł[
Several other phosphorus!based dehydrating systems have been reported[ For example\ Appel et
al[ have shown that a combination of PPh2:CCl3:NEt2 will convert formamides into isocyanides
ð60AG"E#021\ 63JOC0128\ 65LA072\ 77TL0342Ł[ This system has also been used in the preparation of N!
isocyanoiminotriphenylphosphane ð79AG"E#379Ł[ Recently\ this dehydrating system has been modi!
_ed by Ichikawa who used CBr3:PPh2:Pri1NEt ð81JCS"P0#1024Ł[ Ugi and co!workers have reported
Mitsunobu!type conditions "PPh2:dead "diethyl azodicarboxylate## for the dehydration reaction
ð61AG"E#818Ł[ Triphenylphosphine dibromide has been utilized in the dehydration of formamides
to isocyanides ð57LA"607#13Ł\ as have phosphorus trichloride\ phosphorus tribromide\ phosphorus
pentachloride\ and phosphorus pentoxide ð59CB128Ł[
p!Toluenesulfonyl chloride or benzenesulfonyl chloride in conjunction with a base is still a widely
used method for the dehydration of formamides[ A variety of bases have been employed\ including
pyridine ð47JOC0110\ 75CJC1364\ 78S607\ 81JOC1907Ł and quinoline ð52JCS3179\ 62OSC"4#662Ł[ A par!
ticularly interesting use of the TsCl:pyridine dehydrating system was reported by Ugi and co!
workers who described the preparation of a variety of macromolecular isocyanides from polymer!
bound formamides ð71AG"E#263Ł[ The use of methanesulfonyl chloride:pyridine has also been dis!
closed ð68JA0597\ 68TL1634Ł[
The application of Vilsmeier!type dehydrating systems is also well documented in the synthesis
of isocyanides from formamides[ The classical SOCl1:DMF mixture\ generating chloro!
dimethylformiminium chloride at low temperature\ followed by addition of the formamide and then
Na1CO2 was used by Walborsky ð59CB128\ 61JOC076\ 66LA39\ 77OSC"5#640Ł[ A more recent variation
on this method utilizes 1!chloro!2!ethylbenzoxazolium tetra~uoroborate in the presence of tri!
ethylamine ð66CL586Ł[
A particularly mild dehydrating reagent oxomethylenebis!"2H¦!imidazolium# bis"methane!
sulfonate# was recently described by Ugi et al[ ð71JCR"S#68Ł[ This reagent\ which is prepared in situ by
the addition of methanesulfonic acid to oxomethylenebis"imidazole#\ is reported to be particularly ef!
fective in the preparation of homochiral isocyanoesters\ which are prone to racemization "Equation "2##[
O +
CO2Me CO2Me NH
+ +
+ N N + 2 Ms– + CO2
HN NH
Ph NHCHO Ph NC N
H (3)
2 Ms–
Very recently\ Baldwin et al[ have reported the use of tri~uoromethanesulfonic anhydride in
conjunction with diisopropylethylamine at −67>C as a highly e}ective method for the dehydration
of functionalized formamides to isocyanides ð89SL592Ł[ Several other examples of this dehydrating
system have subsequently been reported "Equation "3## ð89TL1936\ 80SL604\ 81JCS"P0#1024\ 82TL468\
83CC74Ł[
Isocyanides 586
H H
O (CF3SO2)2O, Pri2NH O
CH2Cl2, –78 °C
(4)
O 86% O
STol STol
NHCHO NC
In addition to the reagents cited above\ a number of less commonly encountered dehydrating
reagents have been employed[ For example\ cyanuric chloride in the presence of K1CO2 has been
used on several occasions ð50AG108\ 60OS"40#20\ 66AG"E#151Ł[ Other reagents in this category include
BF2:HgO ð50JOC1191Ł\ and di!1!pyridyl sul_te:NEt2 ð75TL0814Ł[
R1 R1
NC + base– M+ CN – M+ + base-H (5)
R2 R2
A particularly useful example involves the condensation of a!metallated isocyanides with com!
pounds containing polar multiple bonds[ The initial addition adduct to aldehydes and ketones
contains an electrophilic isocyanide carbon atom which can then be attacked intramolecularly by
the alkoxide[ The resulting heterocycle anion is in equilibrium with the precursor\ the equilibrium
lying on the side of noncyclized anion[ By careful choice of proton source\ either the heterocycle or
the substituted isocyanide can be obtained "Scheme 2#[ Thus\ certain heterocyclic ring systems can
be used as precursors to substituted isocyanides by a deprotonation:reprotonation protocol[
M
CN O CN O– M+
R1 – M+ + R1 R4 N O
R2 R3 R4 R2 R3 R1 R4
R2 R3
AcOH
MeOH
CN OH
R1 R4 N O
R2 R3
R1 R4
R2 R3
Scheme 3
a!Metallated isocyanides have also found extensive use as a!amino anion equivalents ð63AG"E#678\
66AG"E#228\ 68PAC0236Ł[
There are however\ limitations to this approach^ notably sec!alkyl isocyanides without activating
substituents cannot be metallated[ Cyclopropyl and cyclobutyl isocyanides are exceptions to this
rule[ The use of a!metallated isocyanides in synthesis has been reviewed several times ð63AG"E#678\
66AG"E#228\ B!68MI 210!90\ 68PAC0236Ł[
587 Isocyanides and their Heteroanalo`ues
2[10[0[0[4 Use of organometallic isocyanides
The use of TMS!CN in the presence of a catalytic Lewis acid promotes the ring opening of
oxiranes to give either the b!"trimethylsilyl#oxy cyanide or isocyanide[ In general\ harder Lewis
acids "those containing Al# favor the formation of cyanides\ while softer ones "containing zinc\ tin\
gallium and palladium# favour isocyanide formation ð76JOC0902\ 89JOC1905Ł[ This behaviour is a
consequence of the well!known equilibrium between TMS!CN and its isocyanide ð65IC490Ł[
Gassman and co!workers have carried out extensive studies on the ring opening of epoxides with
TMS!CN and ZnI1 to give b!hydroxy isocyanides ð71JA4738\ 72TL544\ 73TL2148Ł[ This methodology
has also been applied by Gassman to the ring opening of oxetanes to yield g!hydroxyisocyanides
ð74TL3860Ł[
Tertiary alkyl halides can also be utilized in transformations of this type[ For example\ Reetz et
al[ have shown that 0!chloroadamantane is converted into 0!isocyanoadamantane by treatment
with TMS!CN and TiCl3 "Equation "5## ð70JOC4334\ 72T850Ł[
TMS-CN, TiCl4
(6)
Cl CH2Cl2, 0 °C NC
78%
Cl3SiH, NEt3
R NCO R NC
Ph2ButSiLi
R NCO R NC + Ph2ButSiO– Li+
O– Li+ OSiButPh2
R R
N SiButPh2 N Li
(6) (7)
Scheme 4
Collman|s reagent\ Na1Fe"CO#3\ has been shown to reduce both isocyanates and isothiocyanates
to the iron carbonyl complex of the isocyanide ð78OM0427Ł[
The reduction of isothiocyanates to isocyanides is more easily achieved than the corresponding
isocyanate reductions\ and can be carried out using a range of di}erent reagents[ These include
triethylphosphine ð0769CB655Ł\ copper ð0762CB109Ł\ triphenyltin hydride ð52JOC0696Ł\ tri!n!butyltin
Isocyanides 588
hydride ð75TL044Ł\ phenylacetyl chloroformamidine ð55CB2052Ł\ and photolysis ð53AG"E#530Ł[ The
use of SmI1 for the reduction of isothiocyanates to isocyanides has also been reported ð81CL0032Ł[
Isocyanide dihalides ð58AG"E#19Ł have proved to be valuable precursors to isocyanides[ They can
be prepared by the addition of the halogen "chlorine and bromine# to the parent isocyanide[ They
are frequently used as a {{protecting group\|| masking the reactivity of the isocyanide[ Isocyanide
dichlorides are the most commonly used dihalides[ Several methods exist for their conversion into
the parent isocyanide[ Aliphatic isocyanide dichlorides are reduced by iodide ion[ The intermediate
isocyanide diiodide is unstable and dissociates spontaneously into the isocyanide and iodine
ð53CA5684Ł[ Triethylphosphine also e}ects the reduction of isocyanide dichlorides ð0769CB655\
51AG737\ 53CA5684Ł as does LiAlH3 ð66JA6256Ł[
The electrochemical reduction of isocyanide dichlorides to give isocyanides has also been disclosed
ð81TL3668Ł[
The reaction of isocyanide dichlorides with certain transition metal complexes yields the cor!
responding isocyanide metal complex ð64AG"E#258\ 67JA3201\ 67TL2916\ 68AG"E#64Ł[ Magnesium metal
was used as the reducing agent by Lentz in the preparation of tri~uoromethyl isocyanide
ð73JFC"13#412Ł[
N N
NaOBr, 0 °C
Ph N Ph NC + 2 N2 + NaBr + H2O (7)
N N
H H2O, CH2Cl2
H
Photochemical methods for the synthesis of isocyanides are rare but they are known[ Boyer
and co!workers have described the photodissociation of formimidoyl cyanides to produce the
corresponding N!alkylisocyanides ð64JCS"P0#0632Ł[ The irradiation of N!n!propyl!0\7!di!t!butyl!4\5!
di!oxo!1\2!benzobicycloocta!1\6!diene gives n!propyl isocyanide in good yields "Equation "7##
ð62CC588Ł[
N Pr
But
O But
hν
PrNC + + CO (8)
But
But
The photolysis of dihydropyrazine derivatives in the presence of rose bengal and oxygen has been
reported to give isocyanides ð77TL0016\ 81JOC1138Ł[
The phase transfer modi_cation of the carbylamine reaction has also been widely used in saturated
aliphatic isocyanide preparation ð77OSC"5#121Ł as have the methods of Ho~e and Lange ð65AG"E#002Ł
and Appel ð60AG"E#021Ł[
In their approach to the natural product 8!isocyanopupukeanane\ a fully saturated isocyanide\
Yamamoto and co!workers used TsCl:pyridine in the dehydration of the N!formamide to the
isocyanide "Equation "09## ð68JA0598Ł[
NHCHO NC
Schollkopf and co!workers have reported the synthesis of 0\1!ethylene diisocyanide\ 0\2!propylene
diisocyanide\ and 0\3!butylene diisocyanide ð79LA17\ 70LA092Ł[ All three diisocyanides were prepared
by the dehydration of the precursor diformamides with phosgene[ The simultaneous preparation of
three isocyano groups by dehydration of the precursor triformamide using diphosgene gives novel
tridentate isocyano ligands "Equation "00## ð80JOM"309#C8\ 80JOM"392#C04\ 81AG"E#0101\ 82AG"E#549Ł[
O
Cl3C
R O Cl R
NHCHO NC (11)
3 3
R = H, Me
OHCHN CN
Tf2O, EtNPri2
(12)
–78 °C
89%
Isocyanides 690
Isocyanide Yield
(%)
77
NC
NC 67
NC
48
NC
69
83
NC
NC
39
NC
67
O
POCl3, Pri2NH, CH2Cl2
R R NC
N
H
In the synthesis of the natural product hapalindole J\ Natsume et al[ chose to use the POCl2:
pyridine dehydrating protocol to convert the precursor formamide into the isocyanide ð78TL0704Ł[
In their synthesis of the natural product 7\04!diisocyano!00"19#!amphilectene ð78JOC0372Ł\ Piers et
al[ utilized the PPh2:CCl3:NEt2 methodology of Appel for the simultaneous dehydration of two N!
formamido groups "Equation "02##[
OHCHN CN
H PPh3, CCl4, NEt3 H
(13)
H H CH2Cl2, 55 °C, 6.5 h H H
OHCHN CN
Corey et al[ have reported the total synthesis of 6\19!diisocyanoadociane[ The introduction of
both isocyano groups was achieved by treatment of the bistri~uoroacetate "7# with TMS!CN in the
presence of TiCl3\ giving a mixture of four diastereoisomeric products "Equation "03## ð76JA176Ł[
CF3OCO CN
H H
(8)
Many naturally occurring isocyanides contain remote unsaturation[ Recent examples of these
can be found in the references ð81TL0482\ 81TL5712Ł[
691 Isocyanides and their Heteroanalo`ues
Schollkopf and co!workers have prepared E!3!phenyl!2!butenyl!isocyanide by treatment of cin!
namyl bromide with the lithio anion of methyl isocyanide ð66LA39Ł[ The preparation of b!ionyl
isocyanide and all trans!retinyl isocyanide using the dehydration of the parent formamides with
SOCl1:DMF:Na1CO2 has also been reported "Equation "04## ð62HCA0560Ł[
i, SOCl2/DMF
NHCHO –40 °C NC
(15)
ii, Na2CO3
88%
Makosza et al[ have shown that nitroarenes react with phenylthiomethyl isocyanide in the presence
of KOBut resulting in the introduction of an isocyanomethyl substituent into positions ortho or
para to the nitro group ð82S0104Ł[ Both chloro and cyano substituents were also present on the aryl
ring "Equation "05##[ Further examples of the synthesis of this class of compounds has been reported
ð89H"20#0744Ł[
NO2 NO2
i, ButOK/DMF
0 °C, 15–30 min
+ PhS NC (16)
NC
ii, CO2, AcOEt
47–72%
Z Z
Z = H, Cl, NO2, CN
i, BunLi
i, BunLi
CN
Br CN
ii, Ph Br
Ph ii, Ph
Ph
Ph Ph CN Ph
Ph Ph Ph Ph
CN Ph Ph CN Ph CN Ph NC
NC NC
Scheme 5
Lentz has reported the synthesis of tri~uoromethylisocyanide by the reduction of the tri~uoro!
methylisocyanide dibromide with magnesium metal ð73JFC"13#412\ 77CB0334\ 78AG"E#0145Ł[ The use of
zinc in DMF has also been reported to e}ect this transformation ð83AG"E#0204Ł[ The preparation
of trichloromethyl isocyanide as its chromium pentacarbonyl complex was described by Degel
ð68AG"E#64Ł[ The intriguing sulfur penta~uoride isocyanide has recently been prepared by a similar
reductive process "Equation "07## ð78AG"E#0145Ł[
Br Mg, THF
N F5S NC (18)
F5S Br
I I
AgOCN Cl3SiH
I2 HNPri2, CH2Cl2
NCO NC
Scheme 6
a!Acyloxy isocyanides were _rst reported by Ho~e\ who treated benzoyl bromide with silver
cyanide in acetone[ The free isocyanide is liberated by treatment with KCN[ In most cases the
products could be isolated\ although they became {{dark and resinous at room temperature and in
the presence of air|| "Equation "19## ð63AG"E#565\ 66AG"E#616Ł[
O O Br O i, AgCN NC O
+ (20)
Ph Br O Ph ii, KCN O Ph
693 Isocyanides and their Heteroanalo`ues
Acyl isocyanides were synthesized only relatively recently[ Ho~e and Lange have reported that
treatment of acyl iodides with silver cyanide yielded the corresponding acyl isocyanides ð66AG"E#151Ł[
These are highly unstable compounds that are best stored and used in solution "Equation "10##[
O AgCN O
(21)
R I R NC
The a!epoxy isocyano group is a highly unusual functional group[ There are only three natural
products\ isonitrin C "trichoviridin# ð65CPB721\ 79T404\ 71ABC0792Ł\ aerocyanidin ð77JAN343Ł and
cavernoisonitrile ð81TL5712Ł\ known to contain this moiety[ Schollkopf et al[ have reported that
ester!substituted a!epoxy isocyanides can be prepared by the conjugate addition of basic peroxide
to a!isocyano acrylates "Equation "11## ð73LA597Ł[
R1 NC O
30% H2O2
R1 NC (22)
NaOH, MeOH CO2Me
R2 CO2Me R2
Recently\ Baldwin and O|Neil have developed a more general route to this class of compounds
ð89TL1936Ł[ Epoxidation of a\b!unsaturated formamides with dimethyldioxirane at −67>C\ followed
by in situ dehydration of the intermediate epoxy formamide with tri~uoromethanesulfonic an!
hydride:Hunig|s base gave the epoxy isocyanides in modest yield "Scheme 6#[
H
NHCHO O O OHCN CN
O (CF3SO2)2O
O
Scheme 7
The pioneering work of Schollkopf et al[ has led to methodology for the preparation of a wide
range of isocyanides bearing oxygen functionality[ In 0857\ these authors reported that treatment
of simple alkyl isocyanides with BunLi at −67>C generated the corresponding a!lithio isocyanide[
Addition of an aldehyde or ketone then gave either the alkene "on warming# or with protonation
the oxazoline[ The source of proton was subsequently found to be important[ Addition of glacial
acetic acid immediately after addition of the carbonyl compound "kinetic protonation# leads to the
b!hydroxy isocyanide[ Protonation in alkaline medium is reversible and gives the oxazoline as the
thermodynamic product "Scheme 7# ð69AG"E#347\ 60AG"E#380Ł[ The crystal structure of an a!lithiated!
isocyanide has been reported ð81AG"E#68Ł[
The a!lithio isocyanide can be alkylated with alkyl bromides or iodides ð66LA39Ł[ The reaction
of a!lithio isocyanides with epoxides and oxetanes\ followed by protonation\ yields the b! and g!
hydroxy isocyanides\ respectively\ with attack occurring at the least hindered carbon "Scheme 8#
ð65LA1094Ł[
With an acidifying substituent on the a!position\ deprotonation can be achieved with weaker
bases ð63AG"E#678Ł[ a!Isocyanoalkanoic esters can be metallated with KOBut in THF[ With ethyl a!
isocyanopropionate\ alkylation leads to 1!isocyano!1!methylalkanoic esters[ From ethylisocyano!
acetate the major product is the dialkylated compound along with starting material ð60AG"E#220\
63AG"E#678\ 74SC156Ł[ When 0\2!dibromopropane is the alkylating agent\ ethyl isocyanoacetate gives
0!isocyanocyclopropanecarboxylate[ The use of other bis!electrophiles has also been described
ð60AG"E#220\ 64CB0479Ł[ The preparation of substituted 0!isocyanocyclopropane carboxylates has
also been achieved by the addition of dimethylsulfoxonium methylide to b!substituted ethyl a!
isocyanoacrylates "Scheme 09# ð62LA500Ł[ A detailed procedure for the preparation of ethyl
isocyanoacetate has been described ð77OSC"5#519Ł[ t!Butyl isocyanoacetate has also been prepared
and utilized in similar transformations ð75AG"E#643Ł[ The preparation of "¦#!7!phenylmenthyl
isocyanoacetate has been described ð81TA28Ł[
Ethyl 1!isocyano!1!lithiopropionate adds to epoxides to give\ after protonation with glacial acetic
acid\ g!isocyanoalcohols[ If no proton source is added and the solution allowed to warm to room
temperature\ cyclization of the alkoxide on to the ester occurs to give the unusual isocyano lactone
"Scheme 00# ð62AG"E#212Ł[
Isocyanides 694
O R3
Li+ R2 O– Li+
BunLi – R2 R3
R1 NC THF, –78 °C R1 NC –78 °C
R1 NC
R3 R3
R2 O– Li+ O R1 R2
–78 °C to RT
R2 + LiOCN
– Li+
N R3
R1 NC R1
AcOH MeOH
–70 °C
R3 R3
R2 OH O
R2
R1 NC R1 N
Scheme 8
O
R5
i, R3
R6 NC OH
–30 °C R1 R5
ii, AcOH R2 R4
R1 R1 R3
BunLi
NC R2 – Li+
THF, –78 °C O
R2 CN i, NC
OH
ii, AcOH R1
Scheme 9
O
+ O R1 R2
R1 NC Me2S –
CH2
Me2S + NC R1 NC
–
R2 CO2Et R1 CO2Et
CO2Et
Scheme 10
O NC NC
AcOH
CN – Li+
EtO2C
–70 °C to 0 °C EtO2C O– Li+ EtO2C OH
CN
O
Scheme 11
695 Isocyanides and their Heteroanalo`ues
The reaction of potassium ethyl isocyanoacetate with ethyl chloroformate gives potassium diethyl
isocyanomalonate\ which can be alkylated in situ by alkyl halides to give the diethyl a!alkyl!a!
isocyanomalonates ð64LA422Ł[
The conjugate addition of the sodium anion of both ethyl isocyanoacetate and ethyl isocyano!
propionate to both a\b!unsaturated esters and nitriles has been described by Schollkopf and co!
workers ð62LA0460\ 62CB2271Ł[ The reaction proceeds in both cases with a catalytic amount of sodium
ethoxide "Scheme 01#[
R2 R3
NaOEt i, NC R3
CN CN R1
NC
CO2Et EtO2C – Na+ EtO2C NC
R1 EtOH R1 ii, AcOH
R2
Scheme 12
The conjugate addition of carbanions to 1!isocyanoacrylic esters provides a useful route for the
preparation of a range of oxygenated isocyanides ð66LA0063Ł[ The carbanions used include Grignard
reagents and diethyl sodium malonate "Scheme 02#[
CO2Et
i,
i, R3MgHal CO2Et R1 R2
R1 NC Et2O, 0 °C R1 NC
NaOEt, EtOH EtO2C NC
R2
R3 CO2Et ii, AcOH R2 CO2Et ii, AcOH
EtO2C CO2Et
Scheme 13
It has been reported that naturally occurring isocyanide acids can be converted into the cor!
responding esters by reaction with alcohols:phenols in the presence of dicyclohexylcarbodiimide
"dcc# and a catalytic amount of 3!dimethylaminopyridine "dmap# ð89JCS"P0#1004Ł[
Van Leusen and co!workers have reported an unusual approach to the preparation of steroidal
isocyanides\ whereby the reduction of the parent a\b!unsaturated isocyanide with NaBH3 gives the
saturated isocyanide in excellent yield ð80S420Ł[
N!Alkylisocyanoacetamides can be readily prepared by the treatment of ethyl isocyanoacetate
with primary amines "Equation "12## ð78S530Ł[
R1NH2
NHR1 (23)
CN CO2Et CN
EtOH
O
The preparation of 1!aryl!1!isocyanoacetamides has also been reported\ by an initial Ugi con!
densation between aromatic aldehydes\ isocyanides and ammonium formate\ followed by dehy!
dration of the N!formamide with POCl2:NEt2 ð89LA824Ł[ This work has been extended to the
preparation of N!substituted 0!isocyano!0!cycloalkanecarboxamides ð80LA732Ł[ The condensation
of chiral amines with methyl isocyanoacetate has also been reported ð74ABC0650Ł[
The synthesis of dialkyl!0!isocyanomethylphosphonates has been reported by Schollkopf and co!
workers ð63LA33\ 70LA698\ 70LA0582\ 73LA599\ 73S0922\ 82LA316Ł[ Schollkopf and co!workers have shown
that the lithium anion of diethyl isocyanomethylphosphonate opens epoxides in the presence of
BF2OEt1 to give diethyl 2!hydroxy!0!isocyanoalkylphosphonates[ Mesylation of the hydroxy group
and base!promoted cyclization then leads to diethyl 0!isocyanocyclopropylphosphonates "Scheme
03# ð82CB316\ 75AG"E#643Ł[
R2 O R2 H
O i, BunLi i, MsCl, NEt3
HO P(OEt)2
CN P(OEt)2 O R1 NC
ii, C5H11tOK
ii, R1 R2
R1 NC H P(OEt)2
H H
BF3•OEt2 O
iii, H2O
Scheme 14
Isocyanides 696
A number of other routes to oxygenated isocyanides have been employed[ The ring opening of
both oxiranes and oxetanes in the presence of TMS!CN and a soft Lewis acid gives access to b! and
g!hydroxy isocyanides\ respectively ð71JA4738\ 72TL544\ 73TL2148\ 74TL3860\ 89OSC"6#183Ł[ A particularly
interesting variation of this reaction involves treatment of the ketone "8# with TMS!CN and TiCl3
to give the oxygenated adamantane "09# "Equation "13## ð89S535Ł[
O O-TMS
TMS-CN, ZnI2 (15 mol%)
(24)
CH2Cl2, ∆, 16 h NC
(9) (10)
The base!promoted ring opening of heterocycles has also found extensive use in the synthesis of
aliphatic isocyanides bearing oxygen functionality[ Meyers et al[ have shown that treatment of
dihydro!0\2!oxazines with BunLi at −67>C\ gives after hydrolytic workup\ g!hydroxy isocyanides
in good yield "Scheme 04# ð58TL4040Ł[
i, BunLi H2O
O O H 2O O– Li+ OH
ii, THF, –78 °C 80%
– Li+
N N NC NC
Scheme 15
1!Oxazolines also participate in this reaction ð66AG"E#228\ 76S582Ł[ A particularly elegant example
of this involves the in situ trapping of the anionic intermediate to generate the product isocyanide
"Scheme 05# ð68JOC1931Ł[
R1 R1 R1 NC R1
BunLi
N R2X R2 NC
N
–78 °C – Li+
EtO EtO EtO O– Li+
O O EtO O
Scheme 16
The direct base!promoted condensations of isocyanides have also been employed\ particularly
with a!isocyanoesters[ Ito has reported the ~uoride!catalyzed Michael addition of a!isocyanoesters
to enones ð78TL0146Ł and Pirrung has used the condensation of a!isocyanoesters with 0\1!dibromo!
propane\ in the synthesis of ethyl 1!methyl!0!isocyanocyclopropanecarboxylate ð75JOC1092Ł[ The
use of palladium!catalyzed allylation of a!isocyanoesters has also been disclosed "Equation "14##
ð76TL3738\ 77TL4040Ł[ Other examples of a!isocyanoester condensations have been reported
ð62LA0460\ 64CB0479\ 75AG"E#643\ 77TL5210Ł[
R1 Pd(PPh3)4
CO2Et + OAc (25)
CN
base, THF R1 CO2Et
NC
Seebach et al[ have reported the synthesis of a number of nonracemic oxygenated isocyanides
using the diphosgene dehydration protocol ð77CB496Ł[ Examples are given in Scheme 06[ Further
examples of homochiral isocyanides bearing oxygen functionality have been reported ð89CB524\
80JCS"P0#1384Ł[
The preparation of remotely hydroxylated isocyanides has been described[ Treatment of g! and
d!hydroxy formamides with phosgene:NEt2 yields the corresponding hydroxyisocyanides in good
yield ð63AG"E#488Ł[ The syntheses of 1!vinyloxyethyl isocyanide ð78ZOR0462Ł and methoxy!
isobutylisocyanide ð78OPP400Ł have also been reported[
Livinghouse et al[ have reported that the conjugate addition of the lithio anion of methyl
isocyanide to cyclohexenone proceeds smoothly\ and that the intermediate enolate anion can be O!
silylated to give the silyl enol ether isocyanide "Equation "15## ð76JA489\ 81JA3978\ 81T1198Ł[ In a
697 Isocyanides and their Heteroanalo`ues
OAc
NC OCHO
N NC
O NC
O
NC NC
N
H
CO2Me
O
O
O H
O
N
N H H
H NC
NC
Scheme 17
further study\ Livinghouse and co!workers examined the factors which a}ect the ratio of 0\1! to
0\3!addition in the reaction of a!metalomethyl isocyanides with a\b!unsaturated ketones ð76S280Ł[
The synthesis of g!isocyano silyl enol ethers has also been described ð78TL0146\ 80JOC6245Ł[
O O-TMS TMS-O NC
i, THF, –78 °C
Li NC + + (26)
ii, TMS-Cl
NC
The preparations of a number of sugars bearing isocyanides have been disclosed[ These include
2!isocyano!2!deoxythymidine ð78S607Ł\ 1\2\3\5!tetra!O!benzoyl!D!glucopyranosyl isocyanide "as a
mixture of anomers# ð65TL2316\ 67JOC0861\ 68TL052\ 74MI 210!90Ł\ 1\2 ] 4\5!di!O!isopropylidene!b!D!
mannofuranosyl isocyanide ð80JOC498Ł\ 1\2\3!tri!O!acetyl!b!D!xylopyranose isocyanide ð75TL044Ł\
and 4!O!tert!butyldimethylsilyl!1\2!O!isopropylidene!a!D!ribofuranosyl isocyanide ð77LA654Ł[ The
preparation of b!lactams bearing an isocyanide group has also been described ð63CC167\ 73TL4964Ł[
PPh3, CCl4
RS NHCHO RS NC
NEt3, CHCl3
60 °C
POCl3
(MeOCH2)2, Et3N
Scheme 18
Isocyanides 698
aniodic oxidation of a!substituted organotin compounds in THF:Bu3NBF3 in the presence of TMS!
CN yields the requisite a!thioisocyanides in good yield "Equation "16## ð83CC438Ł[
Katritzky et al[ have described a ~exible route to a!alkylthio isocyanides ð82S34Ł[ Reaction of
benzotriazole with formamide and an aldehyde gave the intermediate formamides in good yield[
These compounds next react with the sodium salts of both aromatic and aliphatic thiols to generate
the N!"a!alkylthioalkyl#formamides[ Dehydration with POCl2:Na1CO2 then gave the a!alkylthio
isocyanides "Scheme 08#[
Scheme 19
In a study of the stereochemistry of the reactions of b!halothioethers with NaCN and AgCN\
Ruano et al[ have prepared a number of b!methylthioether isocyanides ð74TL2270Ł[
Arenesulfonylmethyl isocyanides have been used extensively in synthesis[ They can be prepared
either by the addition of a!lithiomethyl isocyanide to arenesulfonyl ~uorides ð61LA"655#029\ 61TL1258Ł\
or by the dehydration of the precursor formamide ð61LA"655#029\ 61TL1258\ 74RTC49Ł[ The most widely
used arenesulfonylisocyanide is tosylmethyl isocyanide "TosMIC# "for a detailed procedure for the
preparation of TosMIC\ see ð77OSC"5#876Ł#[ Treatment of TosMIC with a suitable base generates
the a!anion\ which can be quenched with electrophiles[ The most convenient procedure for the
alkylation of TosMIC involves the use of phase transfer catalysis ð64TL2376Ł[ Both mono! and
dialkylation of TosMIC is possible\ and many examples of these reactions exist in the literature
"Scheme 19# ð66TL3118\ 66TL3122\ 79S214\ 70JOC4048\ 71TL4224\ 72SC220\ 72SC268\ 77T6132\ 89TL5106\ 80SL76Ł[
NaH R1 NaH R1
Tos NC NC Tos NC
DMSO DMSO
Tos R2
R1X R2X
Scheme 20
Monoalkylated TosMIC derivatives can also be alkynated by treatment with base and an acid
chloride ð66TL3122Ł[ The use of silicon electrophiles has also been reported ð74RTC066Ł[ The chem!
istry of TosMIC has been reviewed ðB!76MI 210!90Ł[
Hegarty et al[ have shown that treatment of hydrazides with PCl4 gives N!"arylalkyl# amino
isocyanides\ and whose chemistry was then studied in solution ð75CC0085Ł[ The preparation of the
unstable secondary isocyanoamines has been reported "Equation "18## ð70JOC0934Ł[ The pyrolysis
of 3!hydrazonoisoxazol!4"3H#!ones yields the secondary isocyanoamines^ in all cases the substituent
on nitrogen was an aryl or heteroaryl group[
N NHR
∆
RHN NC + CO2 + MeCN (29)
N
O O
The synthesis of imino isocyanides has been disclosed[ They are prepared by the dehydration of
the precursor formyl hydrazone ð51AG388\ 52AG294Ł[ This class of compounds has also been prepared
and isolated "as the dibromo addition adduct# via the bromination of arylidene hydrazinotetrazoles
ð69TL3968Ł[ The preparation of N!isocyanoiminotriphenylphosphane "CN0N1PPh2# has been
reported via the dehydration of formyl hydrazine with PPh2:NEt2:CCl3 ð79AG"E#379Ł[
Ignasiak and co!workers have studied the preparation and chemistry of aryl diazoisocyanides[
These compounds are prepared by the dehydration of formyl triazenes[ It was found that SOCl1:
pyridine was the only dehydrating system that yielded the desired isocyanide "Equation "29##
ð64JCS"P0#1011Ł[
NHCHO SOCl2 NC
(30)
N N N N
Ar Ar
N
The matrix isolation and characterization of the extremely reactive diisocyanogen "CN0NC# has
been described ð77AG"E#825Ł^ however\ subsequent studies showed that the authors had prepared
the isomeric isocyanogen "CN0CN# ð80JA5093Ł[ The _rst preparation of diisocyanogen was later
reported ð81AG"E#0107Ł\ by the thermolysis of norbornadienoneazine[
N!Imidoyl isocyanides have been prepared by the treatment of N!phenylimidoyl bromides with
silver cyanide in chloroform ð66AG"E#616Ł[ Compared to the N!acyl isocyanides\ they are con!
siderably more stable in solution[ However\ attempts to isolate them led to isomerization to the
corresponding imidoyl cyanides[
A number of a!amino isocyanides have been prepared\ including N!"isocyanomethyl#!N!nitro!
propylamine ð70AP"203#348Ł and 0!"isocyanomethyl#!azoles ð72CPB612Ł[ Katritzky et al[ have
reported the synthesis of a!"benzotriazolyl#alkyl isocyanides "Scheme 10# ð89JCS"P0#0736Ł\ and in an
extension of this chemistry\ developed a general route to a!amino isocyanides[ Thus\ treatment of
benzatriazole with formamide and the appropriate aldehyde gives the 0!substituted!N!for!
mylaminobenzatriazole[ On reaction with a secondary amine\ the corresponding 0!substituted N!
"a!amino#formamide is obtained[ These formamides are then dehydrated to the corresponding a!
amino isocyanides using POCl2:Na1CO2 ð82S34Ł[
N O O
N RCHO N H i, POCl3, CH2Cl2
N N
H2NCHO K2 CO3 ii, Na2CO3
N N MeOH N N
96%
H 62%
NHCHO
R R NHCHO R NC
R = Ph
Scheme 21
Katritzky has also described the preparation and use of 0H!benzotriazol!0!yl!methyl isocyanide
"BetMIC# "00# ð78TL5546\ 89JCS"P0#0736\ 80JOC3328\ 80S757Ł[
Schollkopf et al[ have prepared a!isocyanonitriles by the dehydration of a!formylamino nitriles
Isocyanides 600
N
N
N
NC
BetMIC
(11)
using POCl2:NEt2[ The deprotonation and subsequent chemistry of the a!anion has also been
investigated "Equation "20## ð64LA0420Ł[
NHCHO NC
POCl3, NEt3, CH2Cl2
R R (31)
CN CN
The unusual triisocyanide ligand shown in Equation "21# was prepared by dehydration of the
precursor triformamide with diphosgene ð80AG"E#192Ł[
N N
diphosgene
(32)
OHCHN NHCHO NC CN
NHCHO NC
The preparation of isocyanides bearing remote nitrogen functionality has been reported
ð47JOC0488Ł[ Thus treatment of primary amines bearing a remote tertiary amine group with
CHCl2:KOH gave the isocyanide in modest yield "Equation "22##[
AgCN
TMS-I TMS-NC + AgI (34)
Van Leusen and co!workers have published an improved procedure for the preparation of
trimethylsilylmethyl isocyanide ð75SC754Ł[ This useful compound was previously prepared by the
silylation of a!lithio methyl isocyanide ð73SC528Ł[ It was reported that treatment of chloro!
methyltrimethylsilane with formamide gave N!""trimethylsilyl#methyl# formamide in 62)[ De!
hydration using POCl2:Pri1NH then gave the desired product in 64)[ Bis! and tris"trimethyl!
silyl#methyl isocyanide have also been prepared ð69JOM"14#274Ł[
Trialkyl and triaryl isocyanosilanes have been prepared by a number of methods ð41JA4136\
47JA3040Ł^ the unusual disilanyl isocyanide has also been reported ð51JCS437Ł[
Trimethylisocyanogermane and trimethyltinisocyanide have been prepared ð59JOC798Ł by the
treatment of trimethyliodo metal derivative with silver cyanide[ They are both considered to be an
equilibrium mixture of the cyano and isocyano forms[ The synthesis of tetraisocyanogermane has
also been disclosed ð40JA4328\ 47AG545Ł[
601 Isocyanides and their Heteroanalo`ues
Van Leusen and co!workers have prepared a number of boron substituted methyl isocyanides
ð84TL1098Ł[ The synthesis of phosphine functionalized isocyanides as metal ligands has been reported
"Equation "24## ð74JOM"183#C10\ 89JOC3849Ł[
CN Li+ Ph2P– CN
Br PPh2 (35)
Ph Ph
Ph Ph
OH O
NC
CN
NC CO2H
HO
xanthocillin X dermadin
H H OH
O
OH
O O
NC NC
isonitrin A isonitrin B
Scheme 22
As with saturated isocyanides\ a number of general methods have been developed for their
synthesis^ these are given below]
"i# the dehydration of a\b!unsaturated formamides\
"ii# deprotonation and further elaboration of isocyanides and a\b!unsaturated isocyanides\
"iii# b!elimination from functionalized isocyanides\
"iv# base promoted ring opening of heterocycles\
"v# isomerization of allyl isocyanides[
Scheme 23
Baldwin and co!workers have reported that sulfenimines on treatment with formicÐacetic anhy!
dride in the presence of PPh2 and propylene oxide give a\b!unsaturated formamides in good yield
ð89TL1940Ł[ The precursor sulfenimines are accessible from either the parent ketone ð74CC0473Ł or
amine ð68JOC0107Ł[ The subsequent dehydration to give the a\b!unsaturated isocyanide was carried
out using tri~uoromethanesulfonic anhydride in the presence of Hunig|s base "Scheme 13#
ð89SL592Ł[
NH2
STol CHO NC
N HN
PPh3, AcOCHO (CF3SO2)2O, Pri2NEt
or
O , CH2Cl2 CH2Cl2, –78 °C
O
Scheme 24
Barrett and co!workers have recently reported a mild method for the preparation of a\b!unsatu!
rated formamides based upon the Bu2SnH reduction of selenocarbamates ð82CC0659Ł[ The dehy!
dration was e}ected using the methodology of Baldwin ð89SL592Ł or TsCl:pyridine "Scheme 14#[
O O H
NaN3 i, PhMe, ∆ N SePh Bu3SnH, AIBN
Ph
Ph Cl DMF Ph N3 ii, PhSeH, ButOK (cat.) PhH, ∆
O
H
N H (CF3SO2)2O, Pri2NEt
Ph NC
Ph
CH2Cl2, –78 °C
O
Scheme 25
Schollkopf et al[ have developed a general procedure for the synthesis of functionalized a\b!
unsaturated formamides^ these compounds can be readily dehydrated to give the a\b!unsaturated
isocyanides[ The process is known as formylaminomethylenation\ and involves the reaction of a!
metallated isocyanides bearing an acidifying substituent such as CO1R ð61LA"655#005\ 63MI 210!90\
65CB2853Ł\ SO1Ar ð61LA"655#029\ 80RTC391Ł\ P"O#"OR#1 ð81JOC1138Ł\ or 2! or 3!pyridyl ð65LA858Ł\
with aldehydes or ketones in aprotic media "Equation "25##[ Such compounds allow access to a wide
range of highly functionalized a\b!unsaturated isocyanides[ This area has been reviewed ð66AG"E#228\
63AG"E#678Ł[
R1 NC i, base R1 NHCHO
O + (36)
R2 X ii, H+ R2 X
X = CO2Et, SO2Ar, P(O)(OEt)2, 3,4-pyridyl
603 Isocyanides and their Heteroanalo`ues
"ii# Deprotonation and further elaboration of isocyanides and a\b!unsaturated isocyanides
A number of di}erent reagents which can be deprotonated and condensed with an appropriate
electrophile have been developed for the synthesis of a\b!unsaturated isocyanides[ Van Leusen and
co!workers were the _rst to report the use of lithio!a!"trimethylsilyl#tosylmethyl isocyanide
"TosMIC# in the synthesis of a\b!unsaturated isocyanides[ Reaction of lithio!a!"trimethyl!
silyl#tosylmethyl isocyanide with an appropriate aldehyde or ketone yields the a\b!unsaturated
isocyanide in good yield ð71RTC191Ł[ In a related approach based on WadsworthÐEmmons!type
chemistry\ Schollkopf et al[ have described the condensation of the lithio anion of diethyl"isocyano!
methyl#phosphonate with aldehydes to give the a\b!unsaturated isocyanide product ð63LA33\
66LA0056\ 73LA599Ł[
A Peterson!type alkeneation has been used in the synthesis of a\b!unsaturated isocyanides[ The
deprotonation of trimethylsilylmethyl isocyanide with BunLi at −67>C for 0 hour\ followed by
addition of 1\4!dimethoxybenzaldehyde has been reported to give the a\b!unsaturated isocyanide in
59) as a 0 ] 0 mixture of "E#:"Z# isomers ð89S457Ł[
The direct deprotonation of a\b!unsaturated isocyanides bearing an a!hydrogen has been
described by Schollkopf ð66LA0056Ł[ Thus\ treatment of the a\b!unsaturated isocyanide with BunLi
at low temperature\ followed by quenching with an electrophile gives the a!functionalized a\b!
unsaturated isocyanide "Scheme 15# ð66LA0056Ł[
R1 NC BunLi, THF/Et2O R1 NC R1 NC
E+
R2 –110 °C to –70 °C R2 Li R2 E
E+ = TMS-Cl, MeI, ClCO2R, CO2
Scheme 26
O
R2 OLi R2 O-TMS
R2 O MeCOCl TMS-Cl
R1 NC R1 NC
R1 NC
Scheme 27
dbu I2
NC NC NC
Scheme 28
Scheme 29
Scheme 29 shows examples of some of the a\b!unsaturated isocyanides that King and Borodinsky
prepared[
In the total synthesis of the antibiotic O?\O?!dimethylxanthocillin\ Hagedorn et al[ treated the
But NC
NC NC
Pri NC
NC
Scheme 30
605 Isocyanides and their Heteroanalo`ues
precursor dihydroxy formamide with POCl2:pyridine to give the bisb!chloro isocyanide[ Treatment
with KOH:pyridine resulted in elimination of HCl to give the a\b!unsaturated isocyanide "Scheme
20# ð51AG104\ 52AG294\ 54CB082Ł[
CHO OMe OMe
OH HN Cl NC
POCl3 KOH
pyridine pyridine
NH OH NC Cl
MeO OHC MeO
OMe
NC
NC
MeO
Scheme 31
The total synthesis of axisonitrile!3 by Hart et al[\ utilizes an unusual route to the precursor a\b!
unsaturated isocyanide[ Conversion of the a\b!unsaturated carboxylic acid to the corresponding
a\b!unsaturated acyl azide\ followed by Schmidt rearrangement and reduction of the a\b!unsaturated
isocyanate _rst gives the a\b!unsaturated formamide[ Dehydration with TsCl:pyridine then yielded
the natural product "Scheme 21#[
Scheme 32
In their synthesis of erbstatin\ van Leusen et al[ prepared the a\b!unsaturated isocyanide "01#
using the condensation of lithio diethyl "isocyanomethyl#phosphonate with 1\4!dimethoxy!
benzaldehyde[ The product was obtained in 64) yield as a 09 ] 0 mixture of "E#:"Z# isomers
"Equation "26## ð89S457Ł^ for related studies\ see ð76JAN0196Ł[
OMe OMe
CHO NC
O BunLi, THF, –78 °C
+ (37)
(EtO)2P NC
OMe OMe
(12)
The preparation of alkynyl and cyclobutenyl isocyanide complexes have recently been reported
ð83AG"E#229Ł\ and the matrix isolation of ethynyl isocyanide has also been disclosed ð80AG"E#0533Ł[
F
CN F
F FVP, 240 °C
(CO)5CrCN
F F
F
(13)
F F F F F
F F F F
F 70 °C
+
(CO)5 CrCN
F (CO)5Cr C N N C
Cr(CO)5 (CO)5Cr C N N C
Cr(CO)5
F F F F
Scheme 33
are particularly useful\ because the b!bromine can be substituted with a variety of heteroatoms
using a conjugate addition:elimination procedure[ A variety of other substituents on the b!position
were also reported ð77T4356\ 89S670Ł[
R NHCHO R NHCHO R NC
NBS POCl3
Scheme 34
The synthesis of 0!chloro a\b!unsaturated isocyanides has been achieved by the condensation of
the lithio anion of a!chloro!a!isocyanomethylphosphonates with aldehydes and ketones
ð76JAN0088Ł\ and a synthesis of the natural product indsocin which contains an a\b!unsaturated
isocyanide bearing a chloro substituent\ has been reported ð76JAN0191Ł[
i, base
O
ii, R1 NHCHO R1 NC
R1 R2 COCl2, NEt3
CN CO2Et
iii, H+ R2 CO2Et R2 CO2Et
Scheme 35
CHO
NC
O i, NaHMDS (2 equiv.), THF, –78 °C
+
(EtO)2P NC ii, AcOH
N N
H H
B 371
Scheme 36
Van Leusen and co!workers have prepared a number of steroid derivatives that contain an a\b!
unsaturated isocyanide by the condensation of isocyanomethylphosphonate!diethyl esters with the
parent steroidal ketone in the presence of KOBut\ followed by dehydration with POCl2:Pri1NH
ð80RTC282\ 81JOC1138Ł[ The reaction has been developed further by the use of t!butyl "diphenyl!
phosphinyl#isocyanoacetate[ Again\ deprotonation followed by union with an aldehyde or ketone
and subsequent elimination of lithium diphenylphosphinate gives a\b!unsaturated isocyanides
ð70LA88Ł[
Baldwin et al[ have published a number of total syntheses of highly oxygenated a\b!unsaturated
isocyanide containing natural products[ In their total synthesis of isonitrile 169\ the initial elim!
ination of a b!tosyl isocyanide gives an allyl isocyanide\ which is isomerized to the dienyl isocyanide
using dbu and iodine ð73CC022Ł[ The unusual isocyanide spirolactone "05# was prepared via an
initial ring opening of the b!epoxy isocyanide "03#\ followed by an oxidation with pyridinium
chlorochromate "pcc#[ The 0\1 addition of lithium "Z#!b!lithioacrylate to the ketoisocyanide "04#
furnished the spirolactone natural product in low yield "Scheme 26# ð74CC705Ł[
CO2Li
i,
NC NC NC O O
KOBut, THF PCC Li
Scheme 37
The three related natural products] isonitrin A\ isonitrin B "deoxytrichoviridin#\ and isonitrin C
"trichoviridin#\ have all been synthesized by the Baldwin research group ð78SL8\ 80SL440Ł[ Isonitrins
A and B contain an a\b!unsaturated isocyanide in a _ve!membered ring along with a high degree
of oxygenation[ The a\b!unsaturated isocyanide in isonitrin B was prepared by treatment of the
sulfenimine "06# with aceticÐformic anhydride:PPh2:propylene oxide to give the a\b!unsaturated
formamide[ Dehydration to the a\b!unsaturated formamide was e}ected with tri~uoro!
methanesulfonic anhydride in the presence of Hunig|s base at −67>C "Scheme 27# ð78SL8\ 80SL440Ł[
Scheme 38
Fukuyama et al[ have reported the total synthesis of the isocyanide ester "08# whereby the a\b!
unsaturated isocyanide moiety was introduced by treatment of the b!mesyl isocyanide "07# with
base "Equation "27## ð70TL2648Ł[
Isocyanides 608
OMs
O
O
KOBut, THF, PhMe, –78 °C NC
NC (38)
MeO2C
MeO2C
(18) (19)
The synthesis of the antibiotic A!21289A was reported by Schollkopf and co!workers using a
procedure where the a\b!unsaturated isocyanide was prepared by the dehydration of the precursor
a\b!unsaturated formamide utilizing POCl2:NEt2 "Equation "28## ð64CB0479\ 74LA0714Ł[
O O
NHCHO NC
O O
HCO2 H HO H
HCO2 H i, POCl3 (2.2 equiv.), NEt3 (2.2 equiv.) HO H
(39)
H O2CH ii, phosphate buffer (pH 7.3) H OH
H O2CH H OH
O O
OHCHN CN
O O
ANTIBIOTIC A 32390 A
More recently\ Baldwin and co!workers have applied their sulfenimine!based methodology in the
synthesis of analogues of antibiotic A!21289A[ The a\b!unsaturated formamide "10# was prepared
from the sulfenimine "19# as described earlier ð78SL8\ 80SL440Ł[ Dehydration to the a\b!unsaturated
isocyanide was then achieved using tri~uoromethanesulfonic anhydride:Hunig|s base at −67>C
"Scheme 28# ð83CC74Ł[
STol
O O-TBDMS N i, HCO2Ac, PPh3, O , CH2Cl2
O
O
ii, Hg(OAc)2
N O-TBDMS O iii, dbu
TolS
(20)
Kende has prepared the a\b!unsaturated isocyanide "11# by the dehydration of the precursor
formamide with tri~uoromethanesulfonic anhydride:Hunig|s base at −67>C "Equation "39##
ð82TL468Ł[
NC i, BunLi
NC i, BunLi R2 NC
TMS
SR1 ii, TMS-Cl SR1 ii, R2CHO
SR1
Scheme 40
a\b!Unsaturated isocyanides bearing an a!tosyl group are conveniently prepared from the con!
densation of the lithio anion of a!"trimethylsilyl#tosylmethyl isocyanide "TosMIC# with aldehydes
ð71RTC191Ł[ In all the examples given\ an aromatic aldehyde was used "Equation "30##[
NC R NC
THF
R CHO + Li Tos + TMS-OLi (41)
TMS –78 °C to – 30 °C Tos
NC OEt Me2N NC
+ Me2N (42)
CO2Et OEt CO2Et
The unusual a\b!unsaturated isocyanide "12# was prepared by the mono deprotonation of 0\2!
diisocyanopropane with BunLi at −67>C\ followed by intramolecular cyclization of the resulting
anion and in situ trapping with TMS!Cl "Scheme 30# ð79LA17Ł[
Li
Li Li+ TMS NC
TMS-Cl N
NC NC
N N –
CN NC
(23)
Scheme 41
Ph CO2Me
Ph CO2Me PhCH2NH2, Et3N
(43)
50% N NC
Br NC
Ph H
Isocyanides 610
2[10[0[2[2 Isocyanides bearing an a\b!aryl or hetaryl substituent
Ar
–H2O
N CHO Ar NC (44)
H
The reagents of choice are phosgene ð54AG"E#361Ł and diphosgene ð66AG"E#148Ł in the presence
of a tertiary amine[ In a review article by Ugi\ the preparation of over 149 isocyanides is described
by the phosgene method\ many of which are aryl isocyanides ð54AG"E#361\ B!60MI 210!90Ł[ Other
dehydrating reagents that have been used include POCl2 in the presence of a tertiary amine ð52CJC752\
47AG691\ 50OS"30#02\ 55TL770\ 59CB128Ł or secondary amine ð74S399Ł\ PCl4\ P1O4\ ð59CB128Ł\ PPh2Br1
ð57LA"607#13Ł\ PPh2:diethyl azodicarboxylate "dead# ð61AG"E#818Ł\ and PPh2:CCl3:NEt2
ð60AG"E#021Ł[ The use of SOCl1:DMF:Na1CO2 has also found widespread application ð61JOC076Ł[
Miscellaneous dehydrating systems include di!1!pyridyl sul_te:NEt2 ð75TL0814Ł and cyanuric
chloride:K1CO2 ð50AG108Ł[
The treatment of N!aryl thioformamides with cyanogen bromide:NEt2\ has been reported to yield
aryl isocyanides ð53CA"59#4527Ł[
"b# The Hofmann carbylamine reaction[ The treatment of a primary aromatic amine with aque!
ous KOH:CHCl2 under phase transfer conditions leads to the corresponding aryl isocyanide in
reasonable yields ð61AG"E#429\ 61TL0526Ł[ The mechanism of this transformation was discussed in
Section 2[10[0[0[ Other variations have been reported[ Krapcho has described the generation of
dichlorocarbene by thermolysis of sodium trichloroacetate\ followed by its reaction with primary
arylamines to give the isocyanide ð51JOC0978Ł[ Thus\ the reaction is performed under anhydrous
conditions[
The conversion of N!sul_nylarylamines to aryl isocyanides in good yield using CHCl2:KOH:C5H5
has been reported ð66S164Ł[
"c# The reduction of isocyanates\ isothiocyanates and isocyanide dihalides[ Triethylphosphite has
been used in the conversion of aryl isocyanates into aryl isocyanides ð51JOC2540Ł as has 1!phenyl!
2!methyl!0\2\1!oxaphospholidine "Mukaiyama|s reagent# ð54BCJ747Ł[
Baldwin et al[ have reported the preparation of aryl isocyanides by the reduction of the precursor
isocyanate using either diphenyl!t!butylsilyllithium or Cl2SiH:NEt2 ð71CC831Ł[
Aryl isothiocyanates can be converted into aryl isocyanides using a variety of reagents\ including\
triethylphosphine ð0769CB655Ł\ triethylphosphite ð51JOC2540Ł\ triphenyltin hydride ð52JOC0696Ł\
phenylacetyl chloroformamidine ð55CB2052Ł\ and samarium diiodide ð81CL0032Ł[
The transformation of arylisocyanide dihalides into aryl isocyanides has been e}ected with a
number of di}erent reagents\ including phosphines ð51AG737\ 53CA"59#5684Ł\ and potassium iodide
ð53CA"59#5684Ł[ More recently\ the electrochemical reduction of N!aryl isocyanide dichlorides has
been reported to give aryl isocyanides in excellent yields ð81TL3668Ł[
"d# Deprotonation of aryl imidates and aryl heterocycles[ Pornet et al[ have reported that treatment
of aryl imidate ethers with magnesium diisopropylamides yields the corresponding aryl isocyanide
ð54AG"E#691\ 69TL2298\ 60TL856Ł[ In a recent extension of this approach\ it has been disclosed that the
reaction of disubstituted aryl imidate ethers with lithium dialkylamides gives very high yields of
disubstituted aryl isocyanides "Equation "34## ð89CA"001#007364Ł[
611 Isocyanides and their Heteroanalo`ues
R1 R1
LDA, –78 °C
R2 R2 (45)
R3 hexane R3
N OR4 NC
The treatment of benzoxazoles with BunLi at low temperature followed by addition of TMS!Cl\
gives high yields of 1!siloxyaryl isocyanides ð72JOM"135#048Ł[
"e# Abnormal Beckmann rearran`ements[ A number of oxime derivatives have been reported to
give mixtures of cyanides and isocyanides under Beckmann!type conditions[ For example\ treatment
of syn!oximes of aromatic aldehydes with 0\0!diethoxy!0!propene in the presence of BF2 and
HgO gives mixtures of the corresponding aromatic isocyanide "49Ð62) and the cyanides "9Ð12)#
"Equation "35## ð50JOC1191Ł[
F F Br F F
Br Mg
F N F NC (47)
F F F F
The deprotonation of ethyl N!phenylformimidate with BunLi yields phenyl isocyanide "Equation
"37## ð69TL2298Ł[ A further development in this area describes the reaction of substituted aryl imidate
ethers with lithium dialkylamides at low temperature to give substituted aryl isocyanides in excellent
yields ð89CA"001#007364Ł[
Isocyanides 612
Ph BunLi, hexane
N OEt Ph NC (48)
Although not a widely used method\ Farrar has described the preparation of 3!chlorophenyl
isocyanide by treatment of the sodium salt of N!"3!chlorophenyl#dichloromethylsulfonamide with
Na1CO2 at 099>C ð59JCS2947Ł[
N\N?!Diaryl!N!hydroxyformamidines give aryl isocyanides on heating to 069>C ð13JCS"014#76\
13JCS"014#1432Ł\ and Ho
~e has reported that 4!aryl aminotetrazoles give high yields of aryl isocyanides
upon oxidation with sodium hypobromite or lead tetraacetate ð65AG"E#002Ł[
A number of aryl isocyanides bearing a functionalized ortho!methyl substituent have been
prepared[ Substituents include Cl and I ð73IC850Ł\ CN and CO1Me ð63BCJ0075Ł\ ketone ð68JOC1929Ł\
and amide ð68TL0928Ł[ All these compounds were prepared by deprotonation of o!methyl phenyl
isocyanide with BunLi at low temperature and quenching the anion with the appropriate electrophile
"Scheme 31#[
NC NC NC
Scheme 42
Ito and co!workers have described the preparation of o!diisocyanoarenes by dehydration of the
precursor o!di"formamido#arenes using diphosgene ð77S603Ł[ He has also published the synthesis of
the highly hindered 3!"t!butyldimethylsiloxy#!1\5!xylyl isocyanide by dehydration of the precursor
formamide with POCl2:KOBut\ ð59CB128\ 82JOC5655Ł[
Recent interest in the coordination chemistry of multidentate aryl isocyanides has resulted in the
synthesis of a number of novel aryl isocyanides ð82AG"E#549\ 79IC2749Ł[ Thus\ dehydration of the
bisformamide "13# with PPh2:CCl3:Et2N gave the bidentate isocyanide ligand "14# "Equation "38##
ð71IC1067Ł[
O O PPh3, CCl4 O O
(49)
N H H N NEt3
NC CN
OHC CHO
(24) (25)
The trimethylsilyloxy substituted aryl isocyanide "16# has been prepared by treatment of the
precursor benzoxazole "15# with BunLi followed by trapping with TMS!Cl "Scheme 32#
ð73JOM"159#236Ł[
O O O O O O
( )n ( )n ( )n
BunLi TMS-Cl
N N NC CN NC CN
O O OLi OLi O-TMS O-TMS
(26) (27)
Scheme 43
A number of tridentate aryl isocyanide ligands have been synthesized by the dehydration of the
precursor triformamides with diphosgene ð80AG"E#192\ 80CB0572\ 81OM73Ł^ some examples are shown
in "17# and "18#[
N
NC NC
O O
O O O O
CN CN CN CN
(28) (29)
613 Isocyanides and their Heteroanalo`ues
An interesting class of bi! and tetradentate benzoisocyanides has been disclosed by Ito et al[
ð75JOM"292#290Ł[ On treatment of 0\1!dibromoethane with o!lithiomethylphenyl isocyanides\ oxi!
dative dimerization was found to occur\ leading to 0\1!bis"isocyanophenyl#ethanes in good yields[
These intermediates could then be further deprotonated\ and on treatment with one equivalent of
0\1!dibromoethane the cyclic tetra!isocyanide product "29# was isolated "Scheme 33#[
NC Br NC Br
ii, Br NC ii, Br
NC
NC CN
NC
(30)
Scheme 44
Some examples are given in "20#\ "21# and "22#\ and further examples can be found ð54AG"E#361\
B!60MI 210!90Ł[
NC NC
NC
(31) (97%) (32) (97%) (33) (93%)
CN CN
NC
N N
Me2N N N
H Ph
CN NC
CN
NMe Ph
N O
Ph N N N
H Ph Me
Scheme 45
Ugi and co!workers have reported the preparation of a large number of heterocyclic aromatic
isocyanides using his phosgene dehydration protocol\ which again appears to be the method of
choice ð54AG"E#361\ B!60MI 210!90Ł[ The heterocyclic systems include\ furans\ pyridines\ tetrazoles\
quinolines\ benzotriazoles\ benzothiophene and benzothiazoles^ examples are given in Scheme 35[
Ar
COCl2
N CHO Ar NC
H R3N
CN NC
NC
O
N N
(77%) (93%) (71%)
Ph
NC
NC
S
O O2 CN O O
(50%) (60%) (41%)
O NC
S N N
NC N
N N
NC
NC O
(64%) (46%)
Scheme 46
Kozikowski et al[ have disclosed the preparation of the thiophene isocyanide "23# ð80SL543Ł from
the corresponding thiophene amine using the Hofmann carbylamine approach "Equation "40##[
NH2 NC
(34)
TEBA = Triethylbenzylammonium chloride
615 Isocyanides and their Heteroanalo`ues
The unusual 1\3\5!triisocyanotriazinetris"pentacarbonylchromium# has been reported as a stable
compound "24# ð71CC073Ł[
CCr(CO)5
N
N N
N N N
(OC)5CrC CCr(CO)5
(35)
Scheme 47
Copyright # 1995, Elsevier Ltd. All R ights Reserved Comprehensive Organic Functional Group Transformations
References to Volume 3
EXPLANATION OF THE REFERENCE SYSTEM
Throughout this work\ references are designated by a numberÐlettering coding of which the _rst
two numbers denote tens and units of the year of publication\ the next one to three letters denote
the journal\ and the _nal numbers denote the page[ This code appears in the text each time a
reference is quoted^ the advantages of this system are outlined in the Introduction[ The system has
been used previously in {{Comprehensive Heterocyclic Chemistry\|| eds A[ R[ Katritzky and C[ W[
Rees\ Pergamon\ Oxford\ 0873 and is based on that used in the following two monographs] "a# A[ R[
Katritzky and J[ M[ Lagowski\ {{Chemistry of the Heterocyclic N!Oxides\|| Academic Press\
New York\ 0860^ "b# J[ Elguero\ C[ Marzin\ A[ R[ Katritzky and P[ Linda\ {{The Tautomerism of
Heterocycles\|| in {{Advances in Heterocyclic Chemistry\|| Supplement 0\ Academic Press\ New
York\ 0865[
The following additional notes apply]
0[ A list of journal codes in alphabetical order\ together with the journals to which they refer\ is
given immediately following these notes[ Journal names are abbreviated throughout using the
CASSI "Chemical Abstracts Service Source Index# system[
1[ Each volume contains all the references cited in that volume^ no separate lists are given for
individual chapters[
2[ The list of references is arranged in order of "a# year\ "b# journal in alphabetical order of
journal code\ "c# part letter or number if relevant\ "d# volume number if relevant\ "e# page number[
3[ In the reference list the code is followed by "a# the complete literature citation in the con!
ventional manner and "b# the number"s# of the page"s# on which the reference appears\ whether in
the text or in tables\ schemes\ etc[
4[ For nontwentieth!century references the year is given in full in the code[
5[ For journals which are published in separate parts\ the part letter or number is given "when
necessary# in parentheses immediately after the journal code letters[
6[ Journal volume numbers are not included in the code numbers unless more than one volume
was published in the year in question\ in which case the volume number is included in parentheses
immediately after the journal code letters[
7[ Patents are assigned appropriate three!letter codes[
8[ Frequently cited books are assigned codes[
09[ Less common journals and books are given the code {{MI|| for miscellaneous with the whole
code for books pre_xed by the letter {{B!||[
00[ Where journals have changed names\ the same code is used throughout\ e[g[ CB refers to
both Chem[ Ber[ and to Ber[ Dtsch[ Chem[ Ges[
Journal Codes
AAC Antimicrob[ Agents Chemother[
ABC Agric[ Biol[ Chem[
AC Appl[ Catal[
AC"P# Ann[ Chim[ "Paris#
AC"R# Ann[ Chim[ "Rome#
ACH Acta Chim[ Acad[ Sci[ Hung[
616
617 References
UK Usp[ Khim[
UKZ Ukr[ Khim[ Zh[ "Russ[ Ed[#
UP Unpublished Results
URP USSR Pat[
USP US Pat[
WCH Wiadom[ Chem[
YGK Yuki Gosei Kagaku Kyokaishi
YZ Yakugaku Zasshi "J[ Pharm[ Soc[ Jpn[#
ZAAC Z[ Anorg[ Allg[ Chem[
ZAK Zh[ Anal[ Khim[
ZC Z[ Chem[
ZN Z[ Naturforsch[
ZN"A# Z[ Naturforsch[\ Teil A
ZN"B# Z[ Naturforsch[\ Teil B
ZOB Zh[ Obshch[ Khim[
ZOR Zh[ Org[ Khim[
ZPC HoppeÐSeyler|s Z[ Physiol[ Chem[
ZPK Zh[ Prikl[ Khim[
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66JOM"021#248 P[ Krommes and J[ Lorberth^ J[ Or`anomet[ Chem[\ 0866\ 021\ 248[ 371
66JOM"031#044 O[ A[ Kruglaya\ I[ B[ Fedot|eva\ B[ V[ Fedot|ev\ I[ D[ Kalikhman\ E[ I[ Brodskaya and
N[ S[ Vyazankin^ J[ Or`anomet[ Chem[\ 0866\ 031\ 044[ 372
66JOU368 A[ S[ Nakhmanovich and V[ N[ Elokhina^ J[ Or`[ Chem[ USSR "En`l[ Transl[#\ 0866\
02\ 368[ 142
66JOU0878 Y[ G[ Gololobov and L[ I[ Kruglik^ J[ Or`[ Chem[ USSR "En`l[ Transl[#\ 0866\ 02\ 0878[ 452
66JPR434 W[!D[ Rudorf and M[ Augustin^ J[ Prakt[ Chem[\ 0866\ 208\ 434[ 154
66JPR0931 G[ W[ Fischer^ J[ Prakt[ Chem[\ 0866\ 208\ 0931[ 61\ 62
66LA39 U[ Schollkopf\ K[ W[ Henneke\ K[ Madawinata and R[ Harms^ Justus Liebi`s Ann[ Chem[\
0866\ 39[ 585\ 691\ 693
66LA034 E[ Regel and K[!H[ Buchel^ Justus Liebi`s Ann[ Chem[\ 0866\ 034[ 200
66LA0056 U[ Schollkopf\ D[ Sta}orst and R[ Jentsch^ Justus Liebi`s Ann[ Chem[\ 0866\ 0056[ 603\ 604
66LA0063 U[ Schollkopf and R[ Meyer^ Justus Liebi`s Ann[ Chem[\ 0866\ 0063[ 695
66LA0418 R[ Bognar\ J[ Balint and M[ Rakosi^ Justus Liebi`s Ann[ Chem[\ 0866\ 0418[ 257
66MI 206!90 K[ Kurita\ Y[ Kusayama and Y[ Iwakura^ J[ Polym[ Sci[\ Polym[ Chem[ Ed[\ 0866\ 04\ 1052[ 446
66OR"14#62 W[ S[ Wadsworth^ Or`[ React[\ 0866\ 14\ 62[ 084
66OR"14#144 W[ Nagata and M[ Yoshioka^ Or`[ React[\ 0866\ 14\ 144[ 503\ 505\ 522
66OS"45#7 P[ Stutz and P[ A[ Stadler^ Or`[ Synth[\ 0866\ 45\ 7[ 180
66RCR263 A[ N[ Volkova and A[ N[ Nikol|skaya^ Russ[ Chem[ Rev[ "En`l[ Transl[#\ 0866\ 35\ 263[ 563
66RTC068 R[ S[ Sukhai\ J[ Meijer and L[ Brandsma^ Recl[ Trav[ Chim[ Pays!Bas\ 0866\ 85\ 068[ 437
66S0 E[ Breitmaier\ F[!W[ Ullrich\ B[ Pottho}\ R[ Bohme and H[ Bastian^ Synthesis\ 0866\ 0[ 60
66S30 C[ R[ Harrison\ P[ Hodge and W[ J[ Rogers^ Synthesis\ 0866\ 30[ 507
66S015 A[ Loupy\ K[ Sogadji and J[ Seyden!Penne^ Synthesis\ 0866\ 015[ 531
66S134 T[ Kametani\ K[ Takahashi\ T[ Ohsawa and M[ Ihara^ Synthesis\ 0866\ 134[ 554
66S145 L[ Carlsen and F[ Duus^ Synthesis\ 0866\ 145[ 249\ 253
66S164 G[ Domschke\ R[ Beckert and R[ Mayer^ Synthesis\ 0866\ 164[ 584\ 610
66S246 B[!T[ Grobel and D[ Seebach^ Synthesis\ 0866\ 246[ 05\ 19\ 021\ 026\ 180\ 184
66S308 G[ A[ Olah and J[ Welch^ Synthesis\ 0866\ 308[ 2\ 003
66S361 M[ Augustin\ G[ Jahreis and W[ D[ Rudorf^ Synthesis\ 0866\ 361[ 140
66S384 H[ Ahlbrecht and D[ Liesching^ Synthesis\ 0866\ 384[ 546
66S444 G[ H[ Posner and M[ J[ Chapdelaine^ Synthesis\ 0866\ 444[ 008
66S455 R[ J[ K[ Taylor^ Synthesis\ 0866\ 455[ 531
66S478 G[ B[ Bennett^ Synthesis\ 0866\ 478[ 10\ 030
66S596 S[ E[ J[ Glue and I[ T[ Kay^ Synthesis\ 0866\ 596[ 158
66S597 T[ C[ McKenzie^ Synthesis\ 0866\ 597[ 119
66S515 H[ Yoshida\ T[ Ogata and S[ Inokawa^ Synthesis\ 0866\ 515[ 382
66S518 S[ A[ DiBiase and G[ W[ Gokel^ Synthesis\ 0866\ 518[ 531\ 533
66S525 H[ Emde and G[ Simchen^ Synthesis\ 0866\ 525[ 539
66S531 F[ Farina\ M[ V[ Martin\ M[ R[ Martin and F[ Sanchez^ Synthesis\ 0866\ 531[ 57
66S568 R[ Appel and W[ Morbach^ Synthesis\ 0866\ 568[ 384
66S610 K[ Yamamoto\ O[ Minokawa and J[ Tsuji^ Synthesis\ 0866\ 610[ 47
66S662 E[ Mincione\ G[ Ortaggi and A[ Sirna^ Synthesis\ 0866\ 662[ 195
66S665 I[ Rhee\ M[ Ryang\ T[ Watanabe\ H[ Omura\ S[ Murai and N[ Sonoda^ Synthesis\ 0866\
666[ 182
66S666 Y[ Tohda\ K[ Sonogashira and N[ Hagihara^ Synthesis\ 0866\ 666[ 162
66S673 H[ Westmijze and P[ Vermeer^ Synthesis\ 0866\ 673[ 531
66S763 I[ Ryu\ S[ Murai\ I[ Niwa and N[ Sonoda^ Synthesis\ 0866\ 763[ 27\ 062
66S777 R[ S[ Sukhai\ R[ de Jong and L[ Brandsma^ Synthesis\ 0866\ 777[ 441
66T278 J[ L[ Ripoll^ Tetrahedron\ 0866\ 22\ 278[ 427
66T338 H[ Buhl\ B[ Seitz and H[ Meier^ Tetrahedron\ 0866\ 22\ 338[ 441
66T754 P[ D[ Croce and R[ Stradi^ Tetrahedron\ 0866\ 22\ 754[ 356
66T0734 C[ A[ Henrick^ Tetrahedron\ 0866\ 22\ 0734[ 383
66T1916 P[ C[ Traas\ H[ J[ Takken and H[ Boelens^ Tetrahedron\ 0866\ 22\ 1916[ 58
66T1504 B[ M[ Trost^ Tetrahedron\ 0866\ 22\ 1504[ 028
66T2978 J[ Masson\ P[ Metzner and J[ Vialle^ Tetrahedron\ 0866\ 22\ 2978[ 232
66TL006 S[ Sommer^ Tetrahedron Lett[\ 0866\ 006[ 342
66TL148 A[ Tangerman and B[ Zwanenburg^ Tetrahedron Lett[\ 0866\ 148[ 269
66TL670 T[ E[ Cole and R[ Pettit^ Tetrahedron Lett[\ 0866\ 670[ 72\ 091
66TL0998 Y[ Ito\ T[ Hirao\ N[ Ohta and T[ Saegusa^ Tetrahedron Lett[\ 0866\ 0998[ 488
66TL0006 C[ L[ Liotta\ A[ M[ Dabdoub and L[ H[ Zalkow^ Tetrahedron Lett[\ 0866\ 0006[ 523
66TL0114 V[ Reutrakul and W[ Kanghae^ Tetrahedron Lett[\ 0866\ 0114[ 042
66TL0226 T[ Numata and S[ Oae^ Tetrahedron Lett[\ 0866\ 0226[ 524
66TL0266 V[ Reutrakul and W[ Kanghae^ Tetrahedron Lett[\ 0866\ 0266[ 51
66TL0702 F[ Campagna\ A[ Carotti and G[ Casini^ Tetrahedron Lett[\ 0866\ 0702[ 507\ 508
66TL0716 E[ C[ Taylor\ C[ S[ Chiang and A[ McKillop^ Tetrahedron Lett[\ 0866\ 0716[ 035
66TL0850 T[ M[ Dolak and T[ A[ Bryson^ Tetrahedron Lett[\ 0866\ 0850[ 058
66TL1018 P[ C[ Traas\ H[ J[ Takken and H[ Boelens^ Tetrahedron Lett[\ 0866\ 1018[ 53
66TL1314 T[ Nakai\ T[ Mimura and A[ Ari!izumi^ Tetrahedron Lett[\ 0866\ 1314[ 46
667 References
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67OPP190 A[ H[ Lewin\ S[ R[ Parker\ N[ B[ Fleming and F[ I[ Carroll^ Or`[ Prep[ Proced[ Int[\ 0867\
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67OPP100 P[ Herczegh\ R[ Bognar and E[ Timar^ Or`[ Prep[ Proced[ Int[\ 0867\ 09\ 100[ 523
67RTC010 D[ Paquer\ M[ Vazeux and P[ Leriverend^ Recl[ Trav[ Chim[ Pays!Bas\ 0867\ 86\ 010[ 232
67S18 J[ Villiers\ P[ Periot and J[ F[ Normant^ Synthesis\ 0867\ 18[ 125
67S25 P[ Coutrot\ P[ Savignac and F[ Mathey^ Synthesis\ 0867\ 25[ 086
67S52 F[ Huet\ A[ Lechevallier\ M[ Pellet and J[ M[ Conia^ Synthesis\ 0867\ 52[ 8\ 012
67S017 R[ Sauve¼tre\ D[ Masure\ C[ Chuit and J[ F[ Normant^ Synthesis\ 0867\ 017[ 56\ 126
67S028 V[ Calo\ L[ Lopez and D[ S[ Valentino^ Synthesis\ 0867\ 028[ 042
67S039 R[ Bloch^ Synthesis\ 0867\ 039[ 16\ 043
67S031 P[ Pollet and S[ Gelin^ Synthesis\ 0867\ 031[ 101
67S108 J[ K[ Rasmussen and S[ M[ Heilmann^ Synthesis\ 0867\ 108[ 504
67S116 N[ DiBello\ L[ Pellacani and P[ A[ Tardella^ Synthesis\ 0867\ 116[ 042
67S180 S[ Gelin^ Synthesis\ 0867\ 180[ 135
67S290 I[ Ikeda\ Y[ Machii and M[ Okahara^ Synthesis\ 0867\ 290[ 506
67S296 H[ Hauptmann and M[ Mader^ Synthesis\ 0867\ 296[ 68
67S263 G[ Metha^ Synthesis\ 0867\ 263[ 558
67S392 D[ Comins and A[ I[ Meyers^ Synthesis\ 0867\ 392[ 47\ 89\ 090
67S343 H[ Westmijze\ H[ Kleijn and P[ Vermeer^ Synthesis\ 0867\ 343[ 531
67S347 D[ Masure\ C[ Chuit\ R[ Sauvetre and J[ F[ Normant^ Synthesis\ 0867\ 347[ 56\ 126
67S367 D[ C[ Baker and S[ R[ Putt^ Synthesis\ 0867\ 367[ 089
67S410 B[ Krzyzanowska and W[ J[ Stec^ Synthesis\ 0867\ 410[ 328
67S423 E[ Santaniello\ F[ Ponti and A[ Manzocchi^ Synthesis\ 0867\ 423[ 3\ 004
67S424 D[ Daniil\ U[ Merkle and H[ Meier^ Synthesis\ 0867\ 424[ 369
67S591 I[ Kuwajima\ T[ Murobushi and E[ Nakamura^ Synthesis\ 0867\ 591[ 525
67S508 A[ R[ Katritzky and S[ B[ Brown^ Synthesis\ 0867\ 508[ 78
67S560 G[ A[ Olah and D[ Meidar^ Synthesis\ 0867\ 560[ 003
67S561 G[ A[ Olah\ R[ Malhotra\ S[ C[ Narang and J[ A[ Olah^ Synthesis\ 0867\ 561[ 168\ 184\ 185
67S564 L[ A[ M[ Bastiaansen and E[ F[ Godefroi^ Synthesis\ 0867\ 564[ 200
67S567 K[ Schank and C[ Schuhknecht^ Synthesis\ 0867\ 567[ 262
67S691 G[ Olah and Y[ D[ Vankar^ Synthesis\ 0867\ 691[ 507
67S692 G[ Sosnovsky and J[ A[ Krogh^ Synthesis\ 0867\ 692[ 507
67S720 G[ Seitz and R[ Sutrisno^ Synthesis\ 0867\ 720[ 244
67S737 S[ Cacchi^ Synthesis\ 0867\ 737[ 104
67S770 H[ Sughiara\ R[ Tanikaga and A[ Kaji^ Synthesis\ 0867\ 770[ 05\ 21
67S781 K[ Takahashi\ S[ Kimura\ Y[ Ogawa\ K[ Yamada and H[ Iida^ Synthesis\ 0867\ 781[ 306\ 547
67S783 J[ G[ Smith and D[ C[ Irwin^ Synthesis\ 0867\ 783[ 547
67S786 H[ Ahlbrecht and K[ Pfa}^ Synthesis\ 0867\ 786[ 546
67S894 H[ Suzuki\ T[ Fuchita\ A[ Iwasa and T[ Mishina^ Synthesis\ 0867\ 894[ 507
67S808 J[ Jirieny\ D[ M[ Orere and C[ B[ Reese^ Synthesis\ 0867\ 808[ 07\ 022
67SC48 A[ S[ Kende\ D[ Scholz and J[ Schneider^ Synth[ Commun[\ 0867\ 7\ 48[ 029\ 175
67SC100 S[ Danishefsky and C[ F[ Yan^ Synth[ Commun[\ 0867\ 7\ 100[ 27
67SC120 M[ Samson\ and M[ Vandewalle^ Synth[ Commun[\ 0867\ 7\ 120[ 523\ 525
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67SC458 A[ Jonczyk and J[ W<ostowska^ Synth[ Commun[\ 0867\ 7\ 458[ 354
67T0938 D[ L[ J[ Clive^ Tetrahedron\ 0867\ 23\ 0938[ 26\ 062\ 196
67T0540 K[ Omura and D[ Swern^ Tetrahedron\ 0867\ 23\ 0540[ 5\ 007
67T1178 P[ Metzner\ J[ Vialle and A[ Vibet^ Tetrahedron\ 0867\ 23\ 1178[ 232
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72T186 G[ S[ Harris\ D[ Lloyd\ W[ A[ MacDonald and I[ Gosney^ Tetrahedron\ 0872\ 28"1#\ 186[ 499
72T234 V[ V[ Kane\ V[ Singh\ A[ Martin and D[ L[ Doyle^ Tetrahedron\ 0872\ 28\ 234[ 015
72T322 M[ Julia and H[ Mestdagh^ Tetrahedron\ 0872\ 28\ 322[ 308
72T750 G[ M[ Rubottom\ R[ Marrero and J[ M[ Gruber^ Tetrahedron\ 0872\ 28\ 750[ 20\ 43
72T850 M[ T[ Reetz\ I[ Chatziiosi_dis\ H[ Kunzer and H[ Muller!Starke^ Tetrahedron\ 0872\
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72T856 K[ Utimoto\ Y[ Wakabayashi\ T[ Horiie\ M[ Inoue\ Y[ Shishiyama\ M[ Obayashi and
H[ Nozaki^ Tetrahedron\ 0872\ 28\ 856[ 505\ 516\ 522
72T0376 J[ E[ Baldwin and R[ C[ G[ Lopez^ Tetrahedron\ 0872\ 28\ 0376[ 223\ 224
72T0440 M[ Cariou\ G[ Mabon\ G[ Le Guillanton and J[ Simonet^ Tetrahedron\ 0872\ 28\ 0440[ 541\ 543
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72T0666 E[ Bisagni\ N[ Chi Hung and J[ M[ Lhoste^ Tetrahedron\ 0872\ 28\ 0666[ 331
72T1758 D[ L[ Boger^ Tetrahedron\ 0872\ 28\ 1758[ 302\ 303
72T1878 J[ E[ Baldwin\ A[ E[ Derome and P[ D[ Riordan^ Tetrahedron\ 0872\ 28\ 1878[ 587
72T2196 J[ D[ Albright^ Tetrahedron\ 0872\ 28\ 2196[ 026\ 181\ 516
72T2734 P[ S[ Mariano^ Tetrahedron\ 0872\ 28\ 2734[ 319
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74H"12#2958 T[ Shibata\ Y[ Sugimura\ S[ Sato and K[ Kawazoe^ Heterocycles\ 0874\ 12\ 2958[ 523
74H"49#4012 R[ L[ Willer and D[ W[ Moore^ Heterocycles\ 0874\ 49\ 4012[ 318
74HCA051 D[ Seebach\ A[ K[ Beck\ J[ Golinski\ J[ N[ Hay and T[ Laube^ Helv[ Chim[ Acta\ 0874\
57\ 051[ 081
74HCA227 J[ Ackroyd\ M[ Karpf and A[ S[ Dreiding^ Helv[ Chim[ Acta\ 0874\ 57\ 227[ 112\ 162
74HCA634 L[ E[ Overman and S[ Sugai^ Helv[ Chim[ Acta\ 0874\ 57\ 634[ 308
74HCA0124 W[ Fuhrer\ V[ Rasetti and G[ Rihs^ Helv[ Chim[ Acta\ 0874\ 57\ 0124[ 157
74HCA1143 D[ Beer and A[ Vasella^ Helv[ Chim[ Acta\ 0874\ 57\ 1143[ 317
74HOU"E4#500 C[ Grundmann^ Methoden Or`[ Chem[ "Houben!Weyl#\ 0874\ E4\ 500[ 583\ 692
74HOU"E4#0461 C[ Grundmann^ Methoden Or`[ Chem[ "Houben!Weyl#\ 0874\ E4\ 0461[ 576
74HOU"E00#122 E[ Schaumann^ Methoden Or`[ Chem[ "Houben!Weyl#\ 0874\ E00\ 122[ 435
74JA162 M[ Pfau\ G[ Revial\ A[ Guingant and J[ d|Angelo^ J[ Am[ Chem[ Soc[\ 0874\ 096\ 162[ 304
74JA492 W[ D[ Wul} and S[ R[ Gilbertson^ J[ Am[ Chem[ Soc[\ 0874\ 096\ 492[ 169
74JA879 B[ Potter\ K[ Seppelt\ A[ Simon\ E[ M[ Peters and B[ Hettich^ J[ Am[ Chem[ Soc[\ 0874\
096\ 879[ 578
74JA0135 S[ J[ Danishefsky\ E[ Larson\ D[ Askin and N[ Kato^ J[ Am[ Chem[ Soc[\ 0874\ 096\ 0135[ 132
74JA0163 S[ J[ Danishefsky\ E[ Larson and J[ P[ Springer^ J[ Am[ Chem[ Soc[\ 0874\ 096\ 0163[ 133
74JA0615 J[ Drouin\ M[ Boaventura and J[ Conia^ J[ Am[ Chem[ Soc[\ 0874\ 096\ 0615[ 027
74JA1081 I[ Marko\ B[ Ronsmans\ A[!M[ Hesbain!Frisque\ S[ Dumas\ L[ Ghosez\ B[ Ernst and
H[ Greuter^ J[ Am[ Chem[ Soc[\ 0874\ 096\ 1081[ 591
74JA1457 E[!I[ Negeshi\ S[ J[ Holmes\ J[ M[ Tour and J[ A[ Miller^ J[ Am[ Chem[ Soc[\ 0874\ 096\
1457[ 169
74JA1813 C[ P[ Casey\ W[ H[ Miles and H[ Tukada^ J[ Am[ Chem[ Soc[\ 0874\ 096\ 1813[ 408
74JA2061 C[ P[ Casey\ J[ M[ O|Connor and K[ J[ Haller^ J[ Am[ Chem[ Soc[\ 0874\ 096\ 2061[ 434
74JA2227 Y[ L[ Chow and Z[!Z[ Wu^ J[ Am[ Chem[ Soc[\ 0874\ 096\ 2227[ 316
74JA2281 J[ O[ Karlsson\ N[ V[ Nguyen\ L[ D[ Foland and H[ W[ Moore^ J[ Am[ Chem[ Soc[\ 0874\
096\ 2281[ 428
74JA2590 M[ Eyer and D[ Seebach^ J[ Am[ Chem[ Soc[\ 0874\ 096\ 2590[ 080
74JA2617 W[ J[ Evans\ J[ W[ Grate\ L[ A[ Hughes\ H[ Zhang and J[ L[ Atwood^ J[ Am[ Chem[ Soc[\
0874\ 096\ 2617[ 434
74JA3064 G[ A[ Russell\ W[ C[ Law and M[ Zaleta^ J[ Am[ Chem[ Soc[\ 0874\ 096\ 3064[ 053
74JA3221 J[ Dupuis\ B[ Giese\ J[ Hartung and M[ Leising^ J[ Am[ Chem[ Soc[\ 0874\ 096\ 3221[ 510
74JA3228 E[ J[ Corey\ M[ C[ Desai and T[ A[ Engler^ J[ Am[ Chem[ Soc[\ 0874\ 096\ 3228[ 417
74JA3568 R[ K[ Deiter\ C[ A[ Silks\ III\ J[ R[ Fishpaugh and M[ E[ Kastner^ J[ Am[ Chem[ Soc[\ 0874\
096\ 3568[ 106
74JA4108 P[ DeShong\ S[ Ramesh\ V[ Elango and J[ J[ Perez^ J[ Am[ Chem[ Soc[\ 0874\ 096\ 4108[ 120\ 292
74JA4285 R[ Haner\ T[ Laube and D[ Seebach^ J[ Am[ Chem[ Soc[\ 0874\ 096\ 4285[ 426
74JA4888 H[ Strutz\ J[ C[ Dewan and R[ R[ Schrock^ J[ Am[ Chem[ Soc[\ 0874\ 096\ 4888[ 402
74JA5604 C[ F[ Jewel\ Jr[\ L[ S[ Liebeskind and M[ Williamson^ J[ Am[ Chem[ Soc[\ 0874\ 096\
5604[ 433
74JA5620 E[ Block and S[ Ahmad^ J[ Am[ Chem[ Soc[\ 0874\ 096\ 5620[ 258
74JA6068 T[ Hirao\ D[ Misu and T[ Agawa^ J[ Am[ Chem[ Soc[\ 0874\ 096\ 6068[ 016
74JA6193 J[ C[ Scaiano\ W[ G[ McGimpsey and H[ L[ Casal^ J[ Am[ Chem[ Soc[\ 0874\ 096\ 6193[ 203
74JA6486 T[ C[ Hess and H[!P[ Krimmer^ J[ Am[ Chem[ Soc[\ 0874\ 096\ 6486[ 429
74JA6856 P[ A[ Ansto}\ P[ D[ Johnson and A[ W[ Hamson^ J[ Am[ Chem[ Soc[\ 0874\ 096\ 6856[ 119
74JA7955 R[ L[ Danheiser\ J[ M[ Morin\ Jr[ and E[ J[ Salaski^ J[ Am[ Chem[ Soc[\ 0874\ 096\ 7955[ 100
74JCS"P0#156 A[ J[ Pearson\ Y[!S[ Chen\ C[ R[ Han\ S[!Y[ Hsu and T[ Ray^ J[ Chem[ Soc[\ Perkin Trans[
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74JCS"P0#336 J[ Barluenga\ J[ R[ Fernandez and M[ Yus^ J[ Chem[ Soc[\ Perkin Trans[ 0\ 0874\ 336[ 47
74JCS"P0#0050 M[ G[ Pettett and A[ B[ Holmes^ J[ Chem[ Soc[\ Perkin Trans[ 0\ 0874\ 0050[ 256
74JCS"P0#0390 M[ Nitta and T[ Kobayashi^ J[ Chem[ Soc[\ Perkin Trans[ 0\ 0874\ 0390[ 158
74JCS"P0#0406 R[ M[ Paton\ F[ M[ Robertson\ J[ F[ Ross and J[ Crosby^ J[ Chem[ Soc[\ Perkin Trans[ 0\
0874\ 0406[ 575
74JCS"P0#0430 C[ M[ Bladon\ I[ E[ G[ Ferguson\ G[ W[ Kirby\ A[ Lochead and D[ C[ McDougall^ J[ Chem[
Soc[\ Perkin Trans[ 0\ 0874\ 0430[ 222\ 224
74JCS"P0#1012 D[ R[ Boyd\ P[ B[ Coulter\ R[ Hamilton\ N[ T[ Thompson\ N[ D[ Sharma and M[ E[ Stubbs^
J[ Chem[ Soc[\ Perkin Trans[ 0\ 0874\ 1012[ 393
74JCS"P0#1074 P[ L[ Coe\ A[ Sellars and J[ C[ Tatlow^ J[ Chem[ Soc[\ Perkin Trans[ 0\ 0874\ 1074[ 478
74JCS"P0#1082 D[ J[ Buckley and M[ A[ McKervey^ J[ Chem[ Soc[ Perkin Trans[ 0\ 0874\ 1082[ 063\ 123\ 145
74JCS"P0#1396 G[ R[ Clemo and G[ Pattenden^ J[ Chem[ Soc[\ Perkin Trans[ 0\ 0874\ 1396[ 120
74JCS"P0#1556 D[ H[ R[ Barton\ J[ C[ Blazejewski\ B[ Charpiot\ J[ P[ Finet\ W[ B[ Motherwell\
M[ T[ B[ Papoula and J[ C[ Stanforth^ J[ Chem[ Soc[\ Perkin Trans[ 0\ 0874\ 1556[ 034
74JGU15 A[ A[ Leonov\ V[ Y[ Komarov\ A[ V[ Dogadina\ B[ I[ Ionin and A[ A[ Petrov^ J[ Gen[ Chem[
USSR "En`l[ Transl[#\ 0874\ 44\ 15[ 480
74JMC0926 J[ M[ Muchowski and S[ H[ Unger^ J[ Med[ Chem[\ 0874\ 17\ 0926[ 296
74JMC0721 H[ Cairns\ D[ Cox and J[ L[ Syschitzky^ J[ Med[ Chem[\ 0874\ 17\ 0721[ 186
74JOC21 J[ L[ Kice and L[ Weclas^ J[ Or`[ Chem[\ 0874\ 49\ 21[ 254
74JOC022 M[ S[ Mourad\ R[ S[ Varma and G[ W[ Kabalka^ J[ Or`[ Chem[\ 0874\ 49\ 022[ 315
74JOC024 E[ G[ Lewars and S[ Siddiqi^ J[ Or`[ Chem[\ 0874\ 49\ 024[ 429
74JOC064 D[ Caine\ C[ J[ McCloskey and Van Derveer^ J[ Or`[ Chem[\ 0874\ 49\ 064[ 032
74JOC426 I[ Shimizu\ T[ Sugiura and J[ Tsuji^ J[ Or`[ Chem[\ 0874\ 49\ 426[ 122
74JOC432 W[ W[ Sander and O[ L[ Chapman^ J[ Or`[ Chem[\ 0874\ 49\ 432[ 271
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74JOM"183#C10 G[ Facchin\ R[ Campostrini and R[ A[ Michelin^ J[ Or`anomet[ Chem[\ 0874\ 183\ C10[ 601
74LA455 K[ Weinges\ H[ Brachmann\ P[ Stahnecker\ H[ Rodewold\ M[ Nixdorf and H[ Irngartinger^
Liebi`s Ann[ Chem[\ 0874\ 455[ 505
74LA674 U[ Schmidt\ A[ Lieberknecht\ H[ Griesser and H[ Bokens^ Liebi`s Ann[ Chem[\ 0874\
674[ 068\ 073
74LA0714 H[ H[ Wust\ J[ Bardenhagen and U[ Schollkopf^ Liebi`s Ann[ Chem[\ 0874\ 0714[ 608
74LA1294 L[ Capuano and K[ Djokar^ Liebi`s Ann[ Chem[\ 0874\ 1294[ 481\ 482
74M66 E[ Ohler\ M[ El!Badawi and E[ Zbiral^ Monatsh[ Chem[\ 0874\ 005\ 66[ 169
74MAC0644 S[ Asada\ Y[ Kobayashi and S[ Inoue^ Macromol[ Chem[\ 0874\ 075\ 0644[ 517
B!74MI 292!90 T[ L[ Gilchrist^ {{Heterocyclic Chemistry\|| Longman\ Harlow\ 0874[ 093\ 096
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74MI 219!90 V[ Jager\ I[ Muller\ R[ Schohe\ M[ Frey\ R[ Ehrler\ B[ Hafele and D[ Schroter^ Lect[
Heterocycl[ Chem[\ 0874\ 6\ 68[ 572
74MI 210!90 Y[ Araki\ N[ Kobayashi\ K[ Watanabe and Y[ Ishido^ J[ Carbohydr[ Chem[\ 0874\ 3\ 454[ 697
74NJC0 E[ Dunach and H[ B[ Kagan^ Nouv[ J[ Chim[\ 0874\ 0[ 523
74OM0826 J[ H[ Freudenberger and R[ R[ Schrock^ Or`anometallics\ 0874\ 3\ 0826[ 405
701 References
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74PS"14#126 M[ Yoshifuji\ K[ Toyota\ N[ Inamoto\ K[ Hirotsu\ T[ Higuchi and S[ Nagase^ Phosphorus
Sulfur\ 0874\ 14\ 126[ 594
74RTC8 J[ L[ Mieloszynski\ C[ G[ Andrieu\ M[ Schneider and D[ Paquer^ Recl[ Trav[ Chim[
Pays!Bas\ 0874\ 093\ 8[ 241
74RTC49 A[ M[ van Leusen^ Rec[ Trav[ Chim[ Pays!Bas\ 0874\ 093\ 49[ 583\ 698
74RTC066 A[ M[ van Leusen\ J[ Wildeman\ J[ Moskal and A[ W[ van Hemert^ Rec[ Trav[ Chim[
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74S49 G[ Friour\ G[ Cahiez and J[ F[ Normant^ Synthesis\ 0874\ 49[ 100\ 162
74S55 A[ Bender\ D[ Gunther\ L[ Willms and R[ Wingen^ Synthesis\ 0874\ 55[ 060
74S87 V[ P[ Litvinov\ V[ Y[ Mortikov\ Y[ A[ Sharanin and A[ M[ Shestopalov^ Synthesis\
0874\ 87[ 545
74S010 M[!C[ Lasne and J[!L[ Ripoll^ Synthesis\ 0874\ 010[ 122
74S048 Y[ Shen\ W[ Cen and Y[ Huang^ Synthesis\ 0874\ 048[ 68\ 163
74S066 D[ Matthies and I[ Malassa^ Synthesis\ 0874\ 066[ 306
74S073 A[ Saednya^ Synthesis\ 0874\ 073[ 507
74S113 M[ Sato\ K[ Sekiguchi\ H[ Ogasawara and C[ Kaneko^ Synthesis\ 0874\ 113[ 432
74S168 T[ Sasaki\ K[ Mori and M[ Ohno^ Synthesis\ 0874\ 168[ 322
74S242 H[ J[ Anderson and C[ E[ Loader^ Synthesis\ 0874\ 242[ 296
74S253 R[ J[ K[ Taylor^ Synthesis\ 0874\ 253[ 01\ 017
74S399 R[ Obrecht\ R[ Herrmann and I[ Ugi^ Synthesis\ 0874\ 399 585\ 588\ 610\ 611
74S395 Y[ Satoh\ T[ Tayano\ H[ Koshino\ S[ Hara and A[ Suzuki^ Synthesis\ 0874\ 395[ 16
74S528 R[ C[ Haddon\ S[ V[ Chichester and S[ L[ Mayo^ Synthesis\ 0874\ 528[ 252
74S532 H[ Ishibashi^ Synthesis\ 0874\ 532[ 138
74S561 F[ Duus^ Synthesis\ 0874\ 561[ 249\ 253
74S568 F[ Texier!Boullet^ Synthesis\ 0874\ 568[ 395
74S643 H[ Moulines\ T[ Nguyen and C[ Wakselman^ Synthesis\ 0874\ 643[ 56
74S655 J[ C[ Depezay\ Y[ Le Merrer and M[ Saniere^ Synthesis\ 0874\ 655[ 100
74S673 F[ A[ Lakhvich\ T[ S[ Khlebnicova and A[ A[ Akhrem^ Synthesis\ 0874\ 673[ 128
74S851 P[ J[ Stang and V[ Dixit^ Synthesis\ 0874\ 851[ 162
74S856 M[ Tanaka and T[!A[ Kobayashi^ Synthesis\ 0874\ 856[ 395
74S858 P[ G[ Baraldi\ G[ P[ Pollini\ V[ Zanirato\ A[ Barco and S[ Benetti^ Synthesis\ 0874\ 858[ 537
74S0007 M[ A[ Pericas\ F[ Serratosa and E[ Valenti^ Synthesis\ 0874\ 0007[ 136\ 439
74SC046 K[ Mai and G[ Patil^ Synth[ Commun[\ 0874\ 04\ 046[ 505
74SC156 D[ Kalvin\ K[ Ramalingram and R[ Woodard^ Synth[ Commun[\ 0874\ 04\ 156[ 693
74SC224 D[ K[ Dutta\ D[ Prajapati\ J[ S[ Sandhu and J[ N[ Barauah^ Synth[ Commun[\ 0874\ 04\ 224[ 306
74SC260 C[ W[ Spangler\ R[ P[ K[ Tan and R[ S[ Gibson^ Synth[ Commun[\ 0874\ 04\ 260[ 48
74SC332 R[ S[ Varma and G[ W[ Kabalka^ Synth[ Commun[\ 0874\ 04\ 332[ 054
74SC362 B[ Rigo\ S[ Jabre\ F[ Maliar and D[ Couturier^ Synth[ Commun[\ 0874\ 04\ 362[ 548
74SC538 R[ M[ Moriarty and I[ Prakash^ Synth[ Commun[\ 0874\ 04\ 538[ 070
74SC648 H[ J[ Liu and I[ S[ Han^ Synth[ Commun[\ 0874\ 04\ 648[ 010
74SC866 R[ G[ Pews and Z[ Lysenko^ Synth[ Commun[\ 0874\ 04\ 866[ 16
74SC880 G[ Mehta and H[ S[ P[ Rao^ Synth[ Commun[\ 0874\ 04\ 880[ 040
74SC0160 J[ V[ Early and N[ W[ Gilman^ Synth[ Commun[\ 0874\ 04\ 0160[ 209
74SC0214 R[ S[ Varma\ M[ Varma and G[ W[ Kabalka^ Synth[ Commun[\ 0874\ 04\ 0214[ 315
74T316 E[ E[ Aboujaoude\ N[ Collignon and P[ Savignac^ Tetrahedron\ 0874\ 30\ 316[ 49
74T588 J[ E[ Baldwin\ R[ H[ Jones\ C[ Najera and M[ Yus^ Tetrahedron\ 0874\ 30\ 588[ 318
74T708 M[ Regitz and R[ Martin^ Tetrahedron\ 0874\ 30\ 708[ 371
74T0000 S[ Rozen and R[ Filler^ Tetrahedron\ 0874\ 30\ 0000[ 037
74T0774 M[ E[ Hassan\ M[ A[ Magraby and M[ A[ Aziz^ Tetrahedron\ 0874\ 30\ 0774[ 228\ 250
74T0820 J[ E[ Baldwin\ H[ S[ Bansal\ J[ Chondrogianni\ L[ D[ Field\ A[ A[ Taha\ V[ Thaller\
D[ Brewer and A[ Taylor^ Tetrahedron\ 0874\ 30\ 0820[ 601
74T1892 J[ M[ Aizpurua\ M[ Juaristi\ B[ Lecea and C[ Palomo^ Tetrahedron\ 0874\ 30\ 1892[ 3\ 004
74T2124 R[ B[ King and L[ Borodinsky^ Tetrahedron\ 0874\ 30\ 2124[ 604
74T3914 B[ Giese and M[ Horler^ Tetrahedron\ 0874\ 30\ 3914[ 510
74T3338 K[ Kojima\ K[ Koyama and S[ Amemiya^ Tetrahedron\ 0874\ 30\ 3338[ 24
74T3616 D[ Liotta^ Tetrahedron\ 0874\ 30\ 3616[ 26\ 062
74T3648 T[ G[ Back and R[ G[ Kerr^ Tetrahedron\ 0874\ 30\ 3648[ 063
74T3660 H[ J[ Reich\ C[ A[ Hoeger and W[ W[ Willis\ Jr[^ Tetrahedron\ 0874\ 30\ 3660[ 066
74T3710 A[ P[ Kozikowski and A[ Ames^ Tetrahedron\ 0874\ 30\ 3710[ 184\ 291\ 294\ 296\ 298
74T3732 F[ S[ Guziec\ L[ J[ San Filippo\ C[ J[ Murphy\ C[ A[ Moustakis and E[ R[ Cullen^ Tetrahedron\
0874\ 30\ 3732[ 281
74T3750 D[ Seebach\ G[ Calderari and P[ Knochel^ Tetrahedron Lett[\ 0874\ 30\ 3750[ 081
74T3770 D[ Liotta\ M[ Saindane\ C[ Barnum and G[ Zima^ Tetrahedron\ 0874\ 30\ 3770[ 063
74T4950 M[ P[ Cava and M[ I[ Levinson^ Tetrahedron\ 0874\ 30\ 4950[ 235\ 244
74T4282 J[ D[ Coyle^ Tetrahedron\ 0874\ 30\ 4282[ 241
74T4534 H[ Nagashima\ K[ Sato and J[ Tsuji^ Tetrahedron\ 0874\ 30\ 4534[ 007
74T4744 P[ L[ Pauson^ Tetrahedron\ 0874\ 30\ 4744[ 107
74T4768 R[ Noyori and Y[ Hayakawa^ Tetrahedron\ 0874\ 30\ 4768[ 018
74TL36 S[!F[ Chen and P[ S[ Mariano^ Tetrahedron Lett[\ 0874\ 15\ 36[ 303
74TL366 I[ K[ Stamos^ Tetrahedron Lett[\ 0874\ 15\ 366[ 524
74TL692 S[ Wol} and W[ C[ Agosta^ Tetrahedron Lett[\ 0874\ 15\ 692[ 130
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Tetrahedron Lett[\ 0874\ 15\ 722[ 430
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76JOC1877 J[ Tsuji\ T[ Yamada\ I[ Minami\ M[ Yuhara\ M[ Nisar and I[ Shimizu^ J[ Or`[ Chem[\ 0876\
41\ 1877[ 512
76JOC2235 T[ Kawabata\ P[ A[ Grieco\ H[!L[ Sham\ H[ Kim\ J[ Y[ Law and S[ Tu^ J[ Or`[ Chem[\ 0876\
41\ 2235[ 104
76JOC2355 E[ R[ Kroft^ J[ Or`[ Chem[\ 0876\ 41\ 2355[ 368
76JOC2447 Y[!Z[ Huang\ L[ Shi and J[ Yang^ J[ Or`[ Chem[\ 0876\ 41\ 2447[ 59
76JOC2548 G[ Sacripante and G[ Just^ J[ Or`[ Chem[\ 0876\ 41\ 2548[ 510
76JOC2890 F[ J[ Weiberth and S[ S[ Hall^ J[ Or`[ Chem[\ 0876\ 41\ 2890[ 020\ 394
76JOC2894 A[ G[ Schultz\ W[ G[ McMahon and R[ K[ Kullnig^ J[ Or`[ Chem[\ 0876\ 41\ 2894[ 77
76JOC2808 C[ Sha\ J[ Young and T[ Jean^ J[ Or`[ Chem[\ 0876\ 41\ 2808[ 044
76JOC3936 J[ Drew\ M[ Letellier\ P[ Morand and A[ G[ Szabo^ J[ Or`[ Chem[\ 0876\ 41\ 3936[ 59
76JOC3024 K[ Takeda\ S[!G[ Yano\ M[!A[ Sato and E[ Yoshii^ J[ Or`[ Chem[\ 0876\ 41\ 3024[ 50
76JOC3026 J[ B[ Hendrickson and M[ S[ Hussoin^ J[ Or`[ Chem[\ 0876\ 41\ 3026[ 551
76JOC3074 T[ Calogeropoulou\ G[ B[ Hammond and D[ F[ Weimer^ J[ Or`[ Chem[\ 0876\ 41\ 3074[ 087
711 References
76JOC3309 T[ Okazoe\ K[ Takai\ K[ Oshima and K[ Utimoto^ J[ Or`[ Chem[\ 0876\ 41\ 3309[ 050
76JOC3677 S[ Laugraud\ A[ Guingant and J[ D|Angelo^ J[ Or`[ Chem[\ 0876\ 41\ 3677[ 59
76JOC3709 A[ J[ Poss and R[ K[ Belter^ J[ Or`[ Chem[\ 0876\ 41\ 3709[ 199
76JOC3774 J[ E[ McMurray and G[ K[ Bosch^ J[ Or`[ Chem[\ 0876\ 41\ 3774[ 429\ 420
76JOC4915 X[ Creary^ J[ Or`[ Chem[\ 0876\ 41\ 4915[ 049
76JOC4929 J[ S[ Cha\ J[ E[ Kim and K[ W[ Lee^ J[ Or`[ Chem[\ 0876\ 41\ 4929[ 02\ 71\ 83\ 88
76JOC4399 H[ C[ Brown\ J[ S[ Cha\ N[ M[ Yoon and B[ Nazer^ J[ Or`[ Chem[\ 0876\ 41\ 4399[ 02\ 71
76JOC4356 O[ Bortolini\ S[ Campestrini\ F[ Di[ Furia\ G[ Modena and G[ Valle^ J[ Or`[ Chem[\ 0876\
41\ 4356[ 4\ 006
76JOC4417 S[ F[ Martin and D[ E[ Guinn^ J[ Or`[ Chem[\ 0876\ 41\ 4417[ 111
76JOC4469 D[ Perez\ N[ Greenspoon and E[ Keinan^ J[ Or`[ Chem[\ 0876\ 41\ 4469[ 018
76JOM"220#00 A[ Castel\ P[ Riviere\ J[ Satge and M[ Ahbala^ J[ Or`anomet[ Chem[\ 0876\ 220\ 00[ 346
76JOM"227#218 E[ P[ O[ Fuchs\ M[ Hermesdorf\ W[ Schnurr\ W[ Rosch\ H[ Heydt and M[ Regitz^
J[ Or`anomet[ Chem[\ 0876\ 227\ 218[ 578
76JSP"012#365 Y[ Amatatsu\ Y[ Hamada and M[ Tsuboi^ J[ Mol[ Spectrosc[\ 0876\ 012\ 365[ 464
76KGS0583 E[ V[ Dolenko\ V[ A[ Usov\ L[ V[ Timokhina\ T[ L[ Usova\ L[ E[ Protasova and M[ G[
Voronkov^ Khim[ Geterotsikl[ Soedin[\ 0876\ 0583 "Chem[ Abstr[\ 0877\ 098\ 017 659#[ 230
76LA072 L[ Capuano\ K[ Djokar\ N[ Schneider and C[ Wamprecht^ Justus Liebi`s Ann[ Chem[\ 0876\
072[ 475
B!76MI 290!90 D[ J[ Ager^ in {{Umpoled Synthons\|| ed[ T[ A[ Hase\ Wiley\ New York\ 0876\ p[ 08[ 17\ 20\ 32
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B!76MI 290!92 T[ G[ Back^ in {{Organoselenium Chemistry\|| ed[ D[ Liotta\ Wiley!Interscience\ New York\
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76MI 292!90 J[ S[ Cha\ J[ E[ Kim and S[ Y[ Oh^ Bull[ Kor[ Chem[ Soc[\ 0876\ 7\ 202[ 71
76MI 292!91 J[ S[ Cha\ S[ Y[ Oh and J[ E[ Kim^ Bull[ Kor[ Chem[ Soc[\ 0876\ 7\ 290[ 75
B!76MI 293!90 D[ J[ Ager^ in {{Umpoled Synthons\|| ed[ T[ A[ Hase\ Wiley\ New York\ 0876\ p[ 08[ 046\ 059\ 056
B!76MI 293!91 N[ H[ Werstiuk^ in {{Umpoled Synthons\|| ed[ T[ A[ Hase\ Wiley!Interscience\ New York\
0876\ p[ 062[ 057
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p[ 08[ 071
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p[ 166[ 270
B!76MI 298!91 F[ S[ Guziec\ Jr[^ in {{The Chemistry of Organic Selenium and Tellurium Compounds\|| ed[
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B!76MI 298!92 F[ S[ Guziec\ Jr[^ in {{The Chemistry of Organic Selenium and Tellurium Compounds\|| ed[
S[ Patai\ Wiley\ New York\ 0876\ vol[ 1\ p[ 110[ 277
B!76MI 210!90 A[ M[ van Leusen^ in {{Perspectives in the Organic Chemistry of Sulfur\|| eds[ B[ Zwanenburg
and A[ J[ H[ Klunder\ Elsevier Science\ Amsterdam\ 0876\ p[ 008[ 583\ 698
76OM322 A[ Mayer\ M[ F[ Asaro\ M[ A[ Kjelsberg\ K[ S[ Lee and D[ V[ Engen^ Or`anometallics\
0876\ 5\ 322[ 405
76OM782 A[ D[ Horton\ R[ R[ Schrock and J[ H[ Freudenberger^ Or`anometallics\ 0876\ 5\ 782[ 410
76OM0262 J[ S[ Murdzek and R[ R[ Schrock^ Or`anometallics\ 0876\ 5\ 0262[ 402
76OM 0395 R[ T[ Conlin and K[ L[ Bobbitt^ Or`anometallics\ 0876\ 5\ 0395[ 313
76OM0711 M[ J[ Menu\ P[ Desrosiers\ M[ Dartiguenave\ Y[ Dartiguenave and G[ Bertrand^ Or`an!
ometallics\ 0876\ 5\ 0711[ 375
76OPP070 D[ Armesto\ P[ Bosch\ M[ G[ Gallego\ J[ F[ Martin\ M[ J[ Ortiz\ R[ Perezossorio and
A[ Ramos^ Or`[ Prep[ Proced[ Int[\ 0876\ 08\ 070[ 307
76PAC0994 S[ Kim^ Pure Appl[ Chem[\ 0876\ 48\ 0994[ 72
76PS"29#416 M[ Yoshifuji\ K[ Toyota\ K[ Shibayama\ T[ Hashida and N[ Inamoto^ Phosphorus Sulfur\
0876\ 29\ 416[ 594
76RTC378 B[ J[ M[ Jansen\ R[ M[ Peperzak and Ae[ de Groot^ Recl[ Trav[ Chim[ Pays!Bas\ 0876\ 095\
378[ 24
76RTC438 B[ J[ M[ Jansen\ R[ M[ Peprzak and A[ De Groot^ Recl[ Trav[ Chim[ Pays!Bas\ 0876\ 095\
438[ 142
76S0 E[ Breitmaier\ F[ W[ Ullrich\ B[ Pottho}\ R[ Bohme and H[ Bastian^ Synthesis\ 0876\ 0[ 48\ 64
76S26 A[ Fadel\ R[ Yefsah and J[ Salaun^ Synthesis\ 0876\ 26[ 012
76S39 T[ Frejd and T[ Klingstedt^ Synthesis\ 0876\ 39[ 514
76S45 G[ Bram\ A[ Loupy\ M[ C[ Roux!Schmitt\ J[ Sansoulet\ T[ Strzalko and J[ Seyden!Penne^
Synthesis\ 0876\ 45[ 523
76S69 T[ Je}ery^ Synthesis\ 0876\ 69[ 122
76S68 M[ Ceruti\ I[ Degani and R[ Fochi^ Synthesis\ 0876\ 68[ 00
76S048 J[!H[ Youn\ R[ Herrmann and I[ Ugi^ Synthesis\ 0876\ 048[ 24
76S057 A[ Liguori\ G[ Sindona\ G[ Romeo and N[ Uccella^ Synthesis\ 0876\ 057[ 507
76S068 J[!D[ Lou and W[!X[ Lou^ Synthesis\ 0876\ 068[ 46
References 712
76S077 N[ De Kimpe\ W[ De Cock and N[ Schamp^ Synthesis\ 0876\ 077[ 041
76S196 A[ Ichihara^ Synthesis\ 0876\ 196[ 110
76S147 N[ Ono\ I[ Hamamoto\ A[ Kamimura\ A[ Kaji and R[ Tamura^ Synthesis\ 0876\ 147[ 081
76S200 S[ Cadamuro\ I[ Degani\ R[ Fochi\ A[ Gatti and V[ Regondi^ Synthesis\ 0876\ 200[ 172\ 298
76S280 M[ Westling and T[ Livinghouse^ Synthesis\ 0876\ 280[ 697
76S300 A[ A[ Kandil\ T[ M[ Porter and K[ N[ Slessor^ Synthesis\ 0876\ 300[ 528
76S341 J[ T[ Wrobel and E[ Hejchman^ Synthesis\ 0876\ 341[ 523
76S492 M[ Fetizon\ P[ Goulaouic and I[ Hanna^ Synthesis\ 0876\ 492[ 054
76S421 N[ Ono\ M[ Fujii and A[ Kaji^ Synthesis\ 0876\ 421[ 35\ 089
76S520 A[ Sera\ H[ Tani\ I[ Nishiguchi and T[ Hirashima^ Synthesis\ 0876\ 520[ 510
76S537 H[!J[ Cristau\ Y[ Beziat\ C[ E[ Niangoran and H[ Christol^ Synthesis\ 0876\ 537[ 085
76S548 M[ Mikolajczyk and P[ Balczewski^ Synthesis\ 0876\ 548[ 24
76S582 A[ Dondoni\ G[ Fantin\ M[ Fogagnolo\ A[ Medici and P[ Pedrini^ Synthesis\ 0876\ 582[ 696\ 603
76S608 F[ Clerici\ A[ Di Mare\ M[ L[ Gelmi and D[ Pocar^ Synthesis\ 0876\ 608[ 327
76S618 M[ Node\ H[ Nagasawa\ Y[ Naniwa and K[ Fuji^ Synthesis\ 0876\ 618[ 36\ 081
76S713 A[ Kubo\ N[ Saito\ N[ Kawakami\ Y[ Matsuyama and T[ Miwa^ Synthesis\ 0876\ 713[ 308
76S720 R[ V[ Ho}man and G[ A[ Buntain^ Synthesis\ 0876\ 720[ 320
76S785 S[ Apparao and R[ R[ Schmidt^ Synthesis\ 0876\ 785[ 156
76S897 D[ R[ Williams\ R[ D[ Gaston and J[ F[ Hoover^ Synthesis\ 0876\ 897[ 60
76S813 K[ Burger\ H[ Neuhauser and M[ Eggersdorfer^ Synthesis\ 0876\ 813[ 579
76S827 R[ Zhang and Y[ Zhou^ Synthesis\ 0876\ 827[ 528
76S887 A[ Dondoni\ G[ Fautin\ M[ Fogagnolo\ A[ Medici and P[ Pedrini^ Synthesis\ 0876\ 887[ 098
76S0901 R[ Mahrwald\ F[ Thiel\ H[ Schick and H[!J[ Palme^ Synthesis\ 0876\ 0901[ 119
76S0922 E[ Campi\ N[ J[ Fitzmaurice and W[ R[ Jackson^ Synthesis\ 0876\ 0922[ 66
76S0932 T[ Mukaiyama and M[ Murakami^ Synthesis\ 0876\ 0932[ 119
76S0944 P[ F[ Schuda\ C[ B[ Ebner and S[ J[ Potlock^ Synthesis\ 0876\ 0944[ 084\ 119
76S0981 M[ Ohno\ S[ Matsuoka and S[ Eguchi^ Synthesis\ 0876\ 0981[ 162
76S0985 T[ Hiiro\ N[ Kambe\ A[ Ogawa\ N[ Miyoshi\ S[ Murai and N[ Sonoda^ Synthesis\ 0876\
0985[ 065
76S0002 J[ Cossy^ Synthesis\ 0876\ 0002[ 021
76S0015 S[ Bernasconi\ G[ Jommi\ S[ Montanari and M[ Sisti^ Synthesis\ 0876\ 0015[ 058
76SC044 B[ C[ Rano and D[ C[ Sarkar^ Synth[ Commun[\ 0876\ 06\ 044[ 50
76SC332 H[ A[ Stefani\ J[ V[ Comasseto and N[ Petragnani^ Synth[ Commun[\ 0876\ 06\ 332[ 066
76SC712 R[ Davis^ Synth[ Commun[\ 0876\ 06\ 712[ 060
76SC842 D[ Y[ Kim and D[ Y[ Oh^ Synth[ Commun[\ 0876\ 06\ 842[ 528
76SC872 H[ J[ Monteiro^ Synth[ Commun[\ 0876\ 06\ 872[ 082
76SC0476 A[ R[ Harris^ Synth[ Commun[\ 0876\ 06\ 0476[ 018
76SC0698 J[ S[ Baum\ D[ A[ Shook\ H[ M[ L[ Davies and H[ D[ Smith^ Synth[ Commun[\ 0876\ 06\
0698[ 082
76T440 D[ H[ R[ Barton\ I[ Fernandez\ C[ S[ Richard and S[ Z[ Zard^ Tetrahedron\ 0876\ 32\ 440[ 316\ 329
76T702 T[ Tanaka\ A[ Hazato\ K[ Bannai\ et al[^ Tetrahedron\ 0876\ 32\ 702[ 081
76T0736 A[ R[ B[ Manas and R[ A[ J[ Smith^ Tetrahedron\ 0876\ 32\ 0736[ 172
76T1598 Y[ G[ Gololobov\ A[ N[ Nesmeyanov\ V[ P[ Lysenko and I[ E[ Boldeskul^ Tetrahedron\
0876\ 32\ 1598[ 267
76T1610 D[ Bernard\ A[ Doutheau and J[ Gore^ Tetrahedron\ 0876\ 32\ 1610[ 129
76T2952 A[ Golebiowski\ U[ Jacobsson and J[ Jurczak^ Tetrahedron\ 0876\ 32\ 2952[ 28
76T2834 M[ E[ Borredon\ M[ Delmas and A[ Gaset^ Tetrahedron\ 0876\ 32\ 2834[ 262
76T2852 F[ P[ Cossio\ M[ C[ Lopez and C[ Palomo^ Tetrahedron\ 0876\ 32\ 2852[ 3\ 005
76T3186 D[ H[ R[ Barton\ Y[ Herve\ P[ Potier and J[ Thierry^ Tetrahedron\ 0876\ 32\ 3186[ 524
76T3370 P[ Gramatica\ P[ Manitto\ D[ Monti and G[ Speranza^ Tetrahedron\ 0876\ 32\ 3370[ 47
76T3514 G[ Petrillo\ M[ Novi\ G[ Garbarino and C[ Dell|Erba^ Tetrahedron\ 0876\ 32\ 3514[ 553
76T4060 A[ R[ Katritzky\ D[ L[ Ostercamp and T[ I[ Yousaf^ Tetrahedron\ 0876\ 32\ 4060[ 395
76T4170 M[ Watanabe\ E[ Shinoda\ Y[ Shimizu\ S[ Furukawa\ T[ Kuraishi and M[ Iwao^ Tetrahedron\
0876\ 32\ 4170[ 209
76TL20 L[ A[ Paquette\ J[ L[ Romine and H[!S[ Lin^ Tetrahedron Lett[\ 0876\ 17\ 20[ 195
76TL192 T[ Machiguchi\ H[ Otani\ Y[ Ishii and T[ Hasegawa^ Tetrahedron Lett[\ 0876\ 17\ 192[ 241
76TL184 S[ L[ Buchwald and S[ J[ LaMaire^ Tetrahedron Lett[\ 0876\ 17\ 184[ 503
76TL234 S[ V[ Ley and P[ R[ Woodward^ Tetrahedron Lett[\ 0876\ 17\ 234[ 086
76TL260 H[ M[ L[ Davies and L[ V[ T[ Crisco^ Tetrahedron Lett[\ 0876\ 17\ 260[ 262
76TL286 E[ Di}erding\ O[ Vandevelde\ B[ Roekens\ T[ T[ Van and L[ Ghosez^ Tetrahedron Lett[\
0876\ 17\ 286[ 313
76TL394 M[!P[ Teulade and P[ Savignac^ Tetrahedron Lett[\ 0876\ 17\ 394[ 38
76TL353 D[ S[ Kemp and J[ S[ Carter^ Tetrahedron Lett[\ 0876\ 17\ 353[ 519
76TL436 P[ Q[ Huang\ S[ Arseniyadis and H[!P[ Husson^ Tetrahedron Lett[\ 0876\ 17\ 436[ 505
76TL448 C[ M[ Moorho} and D[ F[ Schneider^ Tetrahedron Lett[\ 0876\ 17\ 448[ 120
76TL500 P[ K[ Chakravarty\ P[ Combs\ A[ Roth and W[ J[ Greenlee^ Tetrahedron Lett[\ 0876\ 17\
500[ 086
76TL658 B[ Byrne and M[ Karras^ Tetrahedron Lett[\ 0876\ 17\ 658[ 008
76TL770 I[ Kolodiazhnyi^ Tetrahedron Lett[\ 0876\ 17\ 770[ 438
76TL774 H[ Dhimane\ J[!C[ Pommelet\ J[ Chuche\ G[ Lhommet and M[ Haddad^ Tetrahedron Lett[\
0876\ 17\ 774[ 430
76TL802 A[ Padwa\ D[ N[ Kline and J[ Perumattam^ Tetrahedron Lett[\ 0876\ 17\ 802[ 149
76TL878 N[ Simkins^ Tetrahedron Lett[\ 0876\ 17\ 878[ 61
713 References
76TL0900 M[ T[ H[ Liu\ N[ Soundarajan\ S[ M[ Anand and T[ Ibata^ Tetrahedron Lett[\ 0876\ 17\
0900[ 213
76TL0958 D[ Liotta\ D[ Brown\ W[ Hoekstra and R[ Monahan^ Tetrahedron Lett[\ 0876\ 17\ 0958[ 118
76TL0182 Y[ Ito\ S[ Nishimura and M[ Ishikawa^ Tetrahedron Lett[\ 0876\ 17\ 0182[ 397
76TL0500 B[ M[ Trost and D[ J[ Jebaratnam^ Tetrahedron Lett[\ 0876\ 17\ 0500[ 519
76TL0736 A[ R[ Katritzky and S[ Sengupta^ Tetrahedron Lett[\ 0876\ 17\ 0736[ 046
76TL0746 J[ S[ Prasad and L[ S[ Liebeskind^ Tetrahedron Lett[\ 0876\ 17\ 0746[ 162
76TL0782 A[ Takahashi and M[ Shibasaki^ Tetrahedron Lett[\ 0876\ 17\ 0782[ 48\ 119
76TL0802 S[ Kim and S[ S[ Kim^ Tetrahedron Lett[\ 0876\ 17\ 0802[ 72
76TL1942 C[ Cardellicchio\ V[ Fiandanese\ G[ Marchese and L[ Ronzini^ Tetrahedron Lett[\ 0876\ 17\
1942[ 029\ 174\ 295
76TL1976 G[ Stork and N[ A[ Saccomano^ Tetrahedron Lett[\ 0876\ 17\ 1976[ 109
76TL1988 L[ Castedo\ J[ L[ Mascarnenas and M[ Mairino^ Tetrahedron Lett[\ 0876\ 17\ 1988[ 46
76TL1020 J[ Muzart^ Tetrahedron Lett[\ 0876\ 17\ 1020[ 182
76TL1044 L[ L[ Shi\ W[ J[ Xia\ J[ H[ Yang\ X[ Wen and Y[ Z[ Huang^ Tetrahedron Lett[\ 0876\ 17\
1044[ 085\ 120
76TL1064 C[ L[ Willis^ Tetrahedron Lett[\ 0876\ 17\ 1064[ 51
76TL1122 P[ Deshong and D[ R[ Sidler^ Tetrahedron Lett[\ 0877\ 42\ 1122[ 107
76TL1186 R[ Antonioletti\ F[ Bonadies and A[ Scettri^ Tetrahedron Lett[\ 0876\ 17\ 1186[ 134
76TL1236 C[ Petrier and J[ Luche^ Tetrahedron Lett[\ 0876\ 17\ 1236[ 016
76TL1242 D[ Bacos\ J[ P[ Celerier and G[ Lhommet^ Tetrahedron Lett[\ 0876\ 17\ 1242[ 300
76TL1248 E[ Laurent\ B[ Marquet\ R[ Tardivel and H[ Thiebault^ Tetrahedron Lett[\ 0876\ 17\ 1248[ 038
76TL1272 S[ Murahashi and T[ Shiota^ Tetrahedron Lett[\ 0876\ 17\ 1272[ 321
76TL1278 J[ S[ Cha\ J[ E[ Kim\ S[ Y[ Oh\ J[ C[ Lee and K[ W[ Lee^ Tetrahedron Lett[\ 0876\ 17\ 1278[ 02\ 71
76TL1362 P[ H[ Mazzocchi\ C[ R[ King and H[ L[ Ammon^ Tetrahedron Lett[\ 0876\ 17\ 1362[ 81\ 86
76TL1570 U[ Gruseck and M[ Heuschmann^ Tetrahedron Lett[\ 0876\ 17\ 1570[ 110
76TL1742 J[ M[ Fang and M[ Y[ Chen^ Tetrahedron Lett[\ 0876\ 17\ 1742[ 525
76TL1810 A[ R[ De Lera and W[ H[ Okamura^ Tetrahedron Lett[\ 0876\ 17\ 1810[ 53
76TL2910 M[ Makosza and Z[ Owczarczyk^ Tetrahedron Lett[\ 0876\ 17\ 2910[ 88\ 094
76TL2004 Y[ Lin\ D[ Ma and X[ Lu^ Tetrahedron Lett[\ 0876\ 17\ 2004[ 007\ 107
76TL2044 P[ Clawson and D[ A[ Whiting^ Tetrahedron Lett[\ 0876\ 17\ 2044[ 207
76TL2188 R[ L[ Danheiser and S[ Savariar^ Tetrahedron Lett[\ 0876\ 17\ 2188[ 105
76TL2346 J[!F[ Lavallee and P[ Deslongchamps^ Tetrahedron Lett[\ 0876\ 17\ 2346[ 111
76TL2352 T[ D[ Aicher and Y[ Kishi^ Tetrahedron Lett[\ 0876\ 17\ 2352[ 133
76TL2404 K[ Suzuki\ M[ Miyazawa and G[!I[ Tsuchihashi^ Tetrahedron Lett[\ 0876\ 17\ 2404[ 059
76TL2572 J[ Tsuji and M[ Minato^ Tetrahedron Lett[\ 0876\ 17\ 2572[ 002
76TL2630 J[ Bergman and L[ Venemalm^ Tetrahedron Lett[\ 0876\ 17\ 2630[ 298
76TL2776 P[ T[ Meinke\ G[ A[ Kra}t and J[ T[ Spencer^ Tetrahedron Lett[\ 0876\ 17\ 2776[ 283
76TL2830 R[ J[ P[ Corriu\ G[ F[ Lanneau and M[ Perrot^ Tetrahedron Lett[\ 0876\ 17\ 2830[
03\ 71\ 84\ 091\ 093\ 096
76TL3104 C[!M[ Andersson and A[ Hallberg^ Tetrahedron Lett[\ 0876\ 17\ 3104[ 134
76TL3156 W[ D[ Rudorf and R[ Schwarz^ Tetrahedron Lett[\ 0876\ 17\ 3156[ 140
76TL3182 M[ Miyashita\ T[ Suzuki and A[ Yoshikoshi^ Tetrahedron Lett[\ 0876\ 17\ 3182[ 059
76TL3280 S[ Collins and Y[ Hong^ Tetrahedron Lett[\ 0876\ 17\ 3280[ 020
76TL3284 W[ Flitsch\ K[ Hampel and M[ Hohenhorst^ Tetrahedron Lett[\ 0876\ 17\ 3284[ 157
76TL3446 T[ Yamada\ K[ Goto\ Y[ Mitsuda and J[ Tsuji^ Tetrahedron Lett[\ 0876\ 17\ 3446[ 320
76TL3464 J[ S[ Cha\ J[ E[ Kim\ S[ Y[ Oh and J[ D[ Kim^ Tetrahedron Lett[\ 0876\ 17\ 3464[ 71
76TL3534 D[ S[ Kemp and J[ S[ Carter^ Tetrahedron Lett[\ 0876\ 17\ 3534[ 519\ 510
76TL3634 F[ Camps\ J[ Coll\ J[ M[ Moreto and J[ Torras^ Tetrahedron Lett[\ 0876\ 17\ 3634[ 107
76TL3722 W[ Ando\ Y[ Kumamoto and N[ Tokitoh^ Tetrahedron Lett[\ 0876\ 17\ 3722[ 240
76TL3738 Y[ Ito\ M[ Sawamura\ M[ Matsuoka\ Y[ Matsumoto and T[ Hayashi^ Tetrahedron Lett[\
0876\ 17\ 3738[ 696
76TL4970 J[ A[ Marshall and S[ L[ Crooks^ Tetrahedron Lett[\ 0876\ 17\ 4970[ 111
76TL4004 F[ A[ Davis\ J[ Wei\ A[ C[ Sheppard and S[ Gubernick^ Tetrahedron Lett[\ 0876\ 17\ 4004[ 327
76TL4130 E[ J[ Corey and W[!G[ Su^ Tetrahedron Lett[\ 0876\ 17\ 4130[ 111
76TL4250 J[ M[ Aizpurua\ M[ Oiarbide and C[ Palomo^ Tetrahedron Lett[\ 0876\ 17\ 4250[ 051
76TL4258 G[ Cainelli\ D[ Giacomini\ M[ Panunzio\ G[ Martelli and G[ Spunta^ Tetrahedron Lett[\
0876\ 17\ 4258[ 339\ 345
76TL4402 A[ E[ Vougioukas and H[ B[ Kagan^ Tetrahedron Lett[\ 0876\ 17\ 4402[ 504\ 521
76TL4508 R[ O[ Hutchins and M[ C[ Rutledge^ Tetrahedron Lett[\ 0876\ 17\ 4508[ 328
76TL4780 M[ Shimazaki\ H[ Hara\ K[ Suzuki and G[!I[ Tsuchihashi^ Tetrahedron Lett[\ 0876\ 17\ 4780[ 059
76TL5068 P[ Jimonet\ D[ S[ Grierson and H[!P[ Husson^ Tetrahedron Lett[\ 0876\ 17\ 5068[ 527
76TL5120 J[ S[ Cha\ J[ E[ Kim\ M[ S[ Yoon and Y[ S[ Kim^ Tetrahedron Lett[\ 0876\ 17\ 5120[ 71\ 88
76TL5350 F[ Tubery\ D[ S[ Grierson and H[!P[ Husson^ Tetrahedron Lett[\ 0876\ 17\ 5350[ 244
76TL5358 S[!I[ Murahashi and T[ Shiota^ Tetrahedron Lett[\ 0876\ 17\ 5358[ 527
76TL5538 K[ Okuma\ J[!I[ Sakata\ Y[ Tachibana\ T[ Honda and H[ Ohta^ Tetrahedron Lett[\ 0876\ 17\
5538[ 273\ 283
76YGK121 M[ Hori and T[ Kataoka^ Yuki Gosei Ka`aku Kyokaishi\ 0876\ 34\ 121 "Chem[ Abstr\ 0876\
096\ 125 270#[ 265
77ACS458 T[ Rein\ B[ Akermark and P[ Helquist^ Acta Chem[ Scand[\ 0877\ 31\ 458[ 54
77AG"E#825 T[ van der Does and F[ Bickelhaupt^ An`ew[ Chem[\ Int[ Ed[ En`l[\ 0877\ 16\ 825[ 609
References 714
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77OR"24#0 R[ E[ Gawley^ Or`[ React[\ 0877\ 24\ 0[ 314\ 320
77OSC"5#121 G[ W[ Gokel\ R[ P[ Widera and W[ P[ Weber^ Or`[ Synth[\ Coll[ Vol[\ 0877\ 5\ 121[ 584\ 585\ 699
77OSC"5#137 G[ H[ Posner and C[ E[ Whitten^ Or`[ Synth[\ Coll[ Vol[\ 0877\ 5\ 137[ 029
77OSC"5#223 P[ A[ Wender\ M[ A[ Eissenstat\ N[ Sapuppo and F[ E[ Ziegler^ Or`[ Synth[\ Coll[ Vol[\ 0877\
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77OSC"5#519 G[ D[ Hartman and L[ M[ Weinstock^ Or`[ Synth[\ Coll[ Vol[\ 0877\ 5\ 519[ 585\ 588\ 693
77OSC"5#640 G[ E[ Niznik\ W[ H[ Morrison and H[ M[ Walborsky^ Or`[ Synth[\ Coll[ Vol[\ 0877\ 5\ 640[ 585\ 699
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77PAC472 Y[ Ito^ Pure Appl Chem[\ 0877\ 51\ 472[ 583
77POL0730 A[ D[ Horton and R[ R[ Schrock^ Polyhedron\ 0877\ 6\ 0730[ 410
77RRC72 M[ D[ Gheorghiu\ L[ Parvulescu\ R[ Ceclan\ I[ Manolescu\ D[ Constantinescu\ C[ Florea
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77S38 H[ J[ Bestmann\ M[ Schmidt and R[ Schobert^ Synthesis\ 0877\ 38[ 119
77S029 G[ Zweifel and T[ M[ Shoup^ Synthesis\ 0877\ 029[ 112
77S025 B[ de Ancos\ M[ C[ Maestro\ M[ R[ Martin and F[ Farin½a^ Synthesis\ 0877\ 025[ 547
77S027 S[ El Cherif and L[ Rene^ Synthesis\ 0877\ 027[ 153
77S067 S[ Katayama\ K[ Fukuda\ T[ Watanabe and M[ Yamauchi^ Synthesis\ 0877\ 067[ 262
77S073 B[ L[ Feringa and J[ F[ G[ A[ Jansen^ Synthesis\ 0877\ 073[ 395
77S109 H[ Ahlbrecht and M[ Ibe^ Synthesis\ 0877\ 109[ 116
77S117 T[ Aoyama and T[ Shioiri^ Synthesis\ 0877\ 117[ 191
77S118 M[ A[ Ashwell and R[ F[ W[ Jackson^ Synthesis\ 0877\ 118[ 089
77S163 L[!F[ Tietze\ H[ Meier and E[ Voss^ Synthesis\ 0877\ 163[ 135
77S203 J[ Castells\ F[ Lopez!Calahorra\ M[ Bassedas and P[ Urrios^ Synthesis\ 0877\ 203[ 071
77S205 B[ L[ Feringa\ R[ Hulst\ R[ Rikers and L[ Brandsma^ Synthesis\ 0877\ 205[ 094
77S208 C[ Glidewell\ D[ Lloyd and S[ Metcalfe^ Synthesis\ 0877\ 208[ 085\ 499
77S210 Y[ Shen and Q[ Liao^ Synthesis\ 0877\ 210[ 499
77S283 H[ Suga and H[ Miyake^ Synthesis\ 0877\ 283[ 8
77S306 D[ P[ Curran^ Synthesis\ 0877\ 306[ 181
77S378 D[ P[ Curran^ Synthesis\ 0877\ 378[ 181
77S453 M[ Rambaud\ M[ Bakasse\ G[ Duguay and J[ Villieras^ Synthesis\ 0877\ 453[ 109
77S593 A[ Kasahara\ T[ Izumi and N[ Kudou^ Synthesis\ 0877\ 593[ 122
77S586 S[ Canonica\ M[ Ferrari\ G[ Jommi and M[ Sisti^ Synthesis\ 0877\ 586[ 48
77S603 Y[ Ito\ A[ Ohnishi\ H[ Ohsaki and M[ Murakami^ Synthesis\ 0877\ 603[ 612
77S794 S[ M[ Ali\ Y[ Matsuda and S[ Tanimoto^ Synthesis\ 0877\ 794[ 317
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References 718
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Trans[ 0\ 0889\ 1610[ 025
89JCS"P0#1764 D[ Batty\ D[ Crich and S[ M[ Fortt^ J[ Chem[ Soc[\ Perkin Trans[ 0\ 0889\ 1764[ 025
89JCS"P0#1770 R[ C[ Davis\ T[ J[ Grinter\ D[ Leaver\ R[ M[ O|Neil and G[ A[ Thomson^ J[ Chem[ Soc[\
Perkin Trans[ 0\ 0889\ 1770[ 260
89JCS"P0#2992 T[ Yamamoto\ M[ T[ Imagawa\ Y[ T[ Yabe\ E[ M[ Suwabe and M[ Muraoka^ J[ Chem[
Soc[\ Perkin Trans[ 0\ 0889\ 2992[ 245
89JCS"P0#2064 G[ W[ Kirby and W[ M[ McGregor^ J[ Chem[ Soc[\ Perkin Trans[ 0\ 0889\ 2064[ 234\ 238\ 240\ 258
89JCS"P0#2254 J[ M[ Fang and C[ C[ Chen^ J[ Chem[ Soc[\ Perkin Trans[ 0\ 0889\ 2254[ 527
89JGU502 I[ S[ Zaltsman\ G[ K[ Bespalko\ A[ P[ Marchenko and A[ M[ Pinchuk^ J[ Gen[ Chem[ USSR
"En`l[ Transl[# 0889\ 59\ 502[ 383
89JHC654 I[ O[ Donker\ A[ Gangee and F[ K[ Duah^ J[ Heterocycl[ Chem[\ 0889\ 16\ 654[ 58
89JHC0416 A[ J[ Bridges and J[ P[ Sanchez^ J[ Heterocycl[ Chem[\ 0889\ 16\ 0416[ 209
727 References
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89JOC303 A[ Padwa\ U[ Chiacchio\ Y[ Garreau\ J[ M[ Kassir\ K[ E[ Krumpe and A[ M[ Scho}stall^
J[ Or`[ Chem[\ 0889\ 44\ 303[ 211
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89JOC484 R[ Tamura\ Y[ Kusama and D[ Oda^ J[ Or`[ Chem[\ 0889\ 44\ 484[ 058
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0975[ 310
89JOC0238 A[ F[ Mateos and J[ A[ de la Fuente Blanco^ J[ Or`[ Chem[\ 0889\ 44\ 0238[ 081
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89JOC0848 R[ L[ Danheiser\ R[ F[ Miller\ R[ G[ Brisbois and S[ Z[ Park^ J[ Or`[ Chem[\ 0889\ 44\
0848[ 082\ 362
89JOC1905 M[ B[ Sassaman\ G[ K[ S[ Prakash and G[ A[ Olah^ J[ Or`[ Chem[\ 0889\ 44\ 1905[ 521\ 587
89JOC1126 R[ V[ Stevens and J[ W[ Canary^ J[ Or`[ Chem[\ 0889\ 44\ 1126[ 108
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1310[ 252
89JOC1434 B[ Sain and J[ S[ Sandhu^ J[ Or`[ Chem[\ 0889\ 44\ 1434[ 556
89JOC1441 R[ J[ Mattson\ K[ M[ Pham\ D[ J[ Leuck and K[ A[ Cowen^ J[ Or`[ Chem[\ 0889\ 44\ 1441[ 33\ 077
89JOC1443 T[ Tsuda\ T[ Kiyoi and T[ Saegusa^ J[ Or`[ Chem[\ 0889\ 44\ 1443[ 103
89JOC1485 F[ Bourdon\ J[!L[ Ripoll\ Y[ Vallee\ S[ Lacombe and G[ P_ster!Guillouzo^ J[ Or`[ Chem[\
0889\ 44\ 1485[ 224
89JOC1731 K[ B[ Gloer\ T[ Calogeropoulou\ J[ A[ Jackson and D[ F[ Weimer^ J[ Or`[ Chem[\ 0889\ 44\
1731[ 087
89JOC1816 E[ Keinan\ D[ Perez\ M[ Sahai and R[ Shvily^ J[ Or`[ Chem[\ 0889\ 44\ 1816[ 012
89JOC2926 J[ Sisko and S[ M[ Weinreb^ J[ Or`[ Chem[\ 0889\ 44\ 2926[ 327
89JOC2003 H[ B[ Kwon\ B[ H[ McKee and J[ K[ Stille^ J[ Or`[ Chem[\ 0889\ 44\ 2003[ 132
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89JOC2543 W[ Cabri\ I[ Candiani and A[ Bedeschi^ J[ Or`[ Chem[\ 0889\ 44\ 2543[ 182
89JOC2547 S[ Campestrini\ F[ Di Furia and G[ Modena^ J[ Or`[ Chem[\ 0889\ 44\ 2547[ 164
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Chem[\ 0889\ 44\ 2633[ 258
89JOC2850 Y[ Shen\ H[ Liu and Y[ Chen^ J[ Or`[ Chem[\ 0889\ 44\ 2850[ 299
89JOC3088 P[ Andreoli\ L[ Billi\ G[ Cainelli\ M[ Panunzio\ G[ Martelli and G[ Spunta^ J[ Or`[ Chem[\
0889\ 44\ 3088[ 347
89JOC3199 E[ Schaumann\ S[ Winter!Extra and G[ Ruhter^ J[ Or`[ Chem[\ 0889\ 44\ 3199[ 223\ 238\ 254
89JOC3124 M[ T[ Crimmins and P[ G[ Nantermet^ J[ Or`[ Chem[\ 0889\ 44\ 3124[ 114
89JOC3345 G[ Bartoli\ E[ Marcantoni\ M[ Petrini and R[ Dalpozzo^ J[ Or`[ Chem[\ 0889\ 44\ 3345[ 323
89JOC3386 M[ Ihara\ Y[ Tokunaga and K[ Fukumoto^ J[ Or`[ Chem[\ 0889\ 44\ 3386[ 119
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44\ 3786[ 21
89JOC3849 M[ G[ Hill\ M[ C[ Comstock and K[ R[ Mann^ J[ Or`[ Chem[\ 0889\ 44\ 3849[ 691\ 692\ 601
89JOC4922 R[ J[ Hinkle\ P[ J[ Stang and M[ H[ Kowalski^ J[ Or`[ Chem[\ 0889\ 44\ 4922[ 385
89JOC4947 M[ M[ Midland and R[ W[ Koops^ J[ Or`[ Chem[\ 0889\ 44\ 4947[ 20
89JOC4451 S[ Kiyooka\ Y[ Kaneko\ H[ Matsue\ M[ Hamada and R[ Fujiyama^ J[ Or`[ Chem[\ 0889\
44\ 4451[ 025\ 192
89JOC4567 D[ A[ Evans and G[ C[ Fu^ J[ Or`[ Chem[\ 0889\ 44\ 4567[ 016
89JOC4579 S[ Sengupta and V[ Snieckus^ J[ Or`[ Chem[\ 0889\ 44\ 4579[ 026\ 046\ 071
89JOC4783 M[ T[ Crimmins and R[ O|Mahony^ J[ Or`[ Chem[\ 0889\ 44\ 4783[ 133
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89JOC5050 R[ G[ Harvey\ J[!T[ Hahn\ M[ Bukowska and H[ Jackson^ J[ Or`[ Chem[\ 0889\ 44\ 5050[ 183
89JOM"262#068 A[ C[ Filippou and E[ O[ Fischer^ J[ Or`anomet[ Chem[\ 0889\ 262\ 068[ 581
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89JOM"274#258 J[ C[ Barnes\ W[ Bell\ C[ Glidewell and R[ A[ Howie^ J[ Or`anomet[ Chem[\ 0889\ 274\ 258[ 252
89JOU0531 A[ F[ Khlebnikov\ M[ S[ Novikov and R[ R[ Kostikov^ J[ Or`[ Chem[ USSR "En`l[ Transl[#\
0889\ 15\ 0531[ 485
89JST"127#60 E[ Suzuki\ R[ Ishiguro and F[ Watari^ J[ Mol[ Struct[\ 0889\ 127\ 60[ 258
89KGS0174 L[ A[ Sviridova\ G[ A[ Golubeva\ D[ M[ Antonov and E[ A[ Makeeva^ Khim[ Geterotsikl[
Soedin[\ 0889\ 0174 "Chem[ Abstr[\ 0880\ 003\ 090 813#[ 230
89LA286 W[ Flitsch and M[ Hohenhorst^ Liebi`s Ann[ Chem[\ 0889\ 286[ 157
89LA824 R[ Bossio\ S[ Marcaccini and R[ Pepino^ Liebi`s Ann[ Chem[\ 0889\ 824[ 695
B!89MI 290!90 D[ H[ Rich^ in {{Comprehensive Medicinal Chemistry\|| ed[ C[ Hansch\ Pergamon Press\
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89OPP696 G[ Rosini\ R[ Ballini\ M[ Petrini\ E[ Marotta and P[ Righi^ Or`[ Prep[ Proced[ Int[\ 0889\
11\ 696[ 35\ 080
89OR"27#544 H[ W[ Pinnick^ Or`[ React[\ 0889\ 27\ 544[ 07\ 023
89OR"28#186 T[ T[ Tidwell^ Or`[ React[\ 0889\ 28\ 176[ 5\ 007
89OS"58#047 J[ C[ Towson\ M[ C[ Weismiller\ G[ S[ Lal\ A[ C[ Sheppard and F[ A[ Davis^ Or`[ Synth[\
0889\ 58\ 047[ 060
89OSC"6#16 G[ Ho~e and B[ Lange^ Or`[ Synth[\ Coll[ Vol[\ 0889\ 6\ 16[ 691
89OSC"6#183 P[ G[ Gassman and T[ L[ Guggenheim^ Or`[ Synth[\ Coll[ Vol[\ 0889\ 6\ 183[ 696
89PAC594 G[ Cainelli\ M[ Panunzio\ P[ Andreoli\ G[ Martelli\ G[ Spunta\ D[ Giacomini and E[ Bandini^
Pure Appl[ Chem[\ 0889\ 51\ 594[ 345\ 346\ 347
89PS"38#290 G[ Bertrand\ A[ Igau\ A[ Baceiredo and H[ Grutzmacher^ Phosphorus Sulfur\ 0889\ 38\ 290[ 578
89PS"43#060 J[ Nasser\ E[ About!Jaudet and N[ Collignon^ Phosphorus Sulfur\ 0889\ 43\ 060[ 528
89RTC335 H[ C[ L[ Abbenhuis\ D[ M[ Grove\ P[ van der Sluis\ A[ L[ Spek and G[ van Koten^ Recl[
Trav[ Chim[ Pays!Bas\ 0889\ 098\ 335[ 401
89S0 S[ Servi^ Synthesis\ 0889\ 0[ 29\ 050
89S016 S[ P[ Acharya and R[ A[ Rane^ Synthesis\ 0889\ 016[ 3
89S051 Z[!T[ Huang and X[ Shi^ Synthesis\ 0889\ 051[ 154
89S084 M[ Hojo\ R[ Masuda\ E[ Okada and H[ Yamamoto^ Synthesis\ 0889\ 084[ 154
89S132 N[ G[ Kundhu\ B[ Das and A[ Majumdar^ Synthesis\ 0889\ 132[ 162
89S290 D[ Jacoby\ J[ P[ Celerier\ H[ Petit and G[ Lhommet^ Synthesis\ 0889\ 290[ 385
89S222 D[ Albanese\ D[ Landini and M[ Penso^ Synthesis\ 0889\ 222[ 316\ 329
89S342 W[ S[ Saari and T[ E[ Fisher^ Synthesis\ 0889\ 342[ 39
89S404 A[ M[ Polozov\ N[ A[ Polezhaeva\ A[ H[ Mustaphin\ A[ V[ Khotinen and B[ A[ Arbuzov^
Synthesis\ 0889\ 404[ 199
89S457 J[ Stoelwinder and A[ M[ van Leusen^ Synthesis\ 0889\ 457[ 603\ 605
89S464 T[ Ziegler\ B[ Horsch and F[ E}enberger^ Synthesis\ 0889\ 464[ 517
89S484 N[ De Kimpe and P[ Brunet^ Synthesis\ 0889\ 484[ 041
89S504 H[ Yinglin and H[ Hongwen^ Synthesis\ 0889\ 504[ 068
89S520 M[ Iman\ P[ Bouyssou and J[ Chenault^ Synthesis\ 0889\ 520[ 163
89S535 G[ A[ Olah\ R[ Krishnamurti and G[ K[ S[ Prakash^ Synthesis\ 0889\ 535[ 696
89S566 M[ Shimazaki\ Z[!H[ Huang\ M[ Goto and N[ Suzuki^ Synthesis\ 0889\ 566[ 197
89S583 A[ Kamimura and T[ Nagashima^ Synthesis\ 0889\ 583[ 35
89S644 V[ Blanchot\ M[ Fetizon and I[ Hanna^ Synthesis\ 0889\ 644[ 139\ 134
89S657 Y[ Yamada and H[ Yasuda^ Synthesis\ 0889\ 657[ 516\ 523
89S670 K[ Hiramatsu\ K[ Nunami\ K[ Hayashi and K[ Matsumoto^ Synthesis\ 0889\ 670[ 606
89S730 V[ A[ Petrosyan\ M[ E[ Niyazymbetov\ L[ D[ Konyushkin and V[ P[ Litvinov^ Synthesis\
0889\ 730[ 523
89S746 T[ T[ Tidwell^ Synthesis\ 0889\ 09\ 746[ 5\ 007
89S774 G[ Olah and A[ H[ Wu^ Synthesis\ 0889\ 774[ 384
89S784 G[ Bartoli\ C[ Cimarelli\ G[ Palmieri and M[ Bosco^ Synthesis\ 0889\ 784[ 151\ 152
89S882 J[ K[ F[ Geirsson and A[ D[ Gudmundsdottir^ Synthesis\ 0889\ 882[ 119
89S0992 J[ Barluenga\ L[ Llavona\ M[ Yus and J[ M[ Concellon^ Synthesis\ 0889\ 0992[ 041\ 043
89S0922 Y[!H[ Chang\ B[!J[ Uang\ C[!M[ Wu and T[!H[ Yu^ Synthesis\ 0889\ 0922[ 51
89S0948 S[ R[ Hitchcock\ F[ Perron\ V[ A[ Martin and K[ F[ Albizati^ Synthesis\ 0889\ 0948[ 059
89S0017 J[ C[ Jochims\ S[ Hehl and S[ Herzberger^ Synthesis\ 0889\ 0017[ 576
89S0062 A[ R[ Katritzky\ J[ Borowiecka and W[!Q[ Fan^ Synthesis\ 0889\ 0062[ 31
89SC04 Y[ Z[ Jiang\ P[ Guo and G[ L[ Liu^ Synth[ Commun[\ 0889\ 19\ 04[ 304
89SC60 M[ Adachi and T[ Sugasawa^ Synth[ Commun[\ 0889\ 19\ 60[ 553
89SC020 J[ E[ Hernandez\ V[ Samano and V[ Valdes^ Synth[ Commun[\ 0889\ 19\ 020[ 195
89SC272 C[ Giordano and M[ Villa^ Synth[ Commun[\ 0889\ 19\ 272[ 290
89SC288 M[ Navarro\ W[ F[ De Giovani and J[ R[ Romero^ Synth[ Commun[\ 0889\ 19\ 288[ 6\ 019
89SC598 J[ C[ Cochran and M[ G[ Melville^ Synth[ Commun[\ 0889\ 598[ 80\ 86
89SC526 H[ R[ Kim\ E[ K[ Ryu\ J[ H[ Jung and J[ N[ Kim^ Synth[ Commun[\ 0889\ 19\ 526[ 019\ 183
89SC602 A[ Muza}ar and A[ Brossi^ Synth[ Commun[\ 0889\ 19\ 602[ 242
89SC854 D[ Albanese\ D[ Landini\ M[ Penso and G[ Pozzi^ Synth[ Commun[\ 0889\ 19\ 854[ 532
89SC0984 G[ L[ Larson\ J[ A[ Soderquist and M[ R[ Claudio^ Synth[ Commun[\ 0889\ 19\ 0984[ 161
89SC0554 G[ T[ Crisp and T[ P[ Bubner^ Synth[ Commun[\ 0889\ 19\ 0554[ 160
89SC0832 C[ C[ Fortes and E[ A[ Okina^ Synth[ Commun[\ 0889\ 19\ 0832[ 523
739 References
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89SC1140 B[ Mauze and L[ Miginiac^ Synth[ Commun[\ 0889\ 19\ 1140[ 549
89SC1168 A[ S[ Demir\ N[ Camkerten\ H[ Akgun\ C[ Tanyeli\ A[ S[ Mahasneh and D[ S[ Watt^ Synth[
Commun[\ 0889\ 19\ 1168[ 051
89SC1180 X[ Huang and J!H[ Pi^ Synth[ Commun[\ 0889\ 19\ 1180[ 524
89SC1248 C[ M[ Adams and J[ E[ Schemenaur^ Synth[ Commun[\ 0889\ 19\ 1248[ 313
89SC1342 G[ W[ Kabalka\ R[ D[ Pace and P[ P[ Wadgaonkar^ Synth[ Commun[\ 0889\ 19\ 1342[ 315
89SC1426 A[ Alberola\ J[ M[ Andres\ A[ Gonzalez and R[ Pedrosa^ Synth[ Commun[\ 0889\ 19\
1426[ 141
89SC1454 M[ L[ Scarpati\ A[ Bianco\ L[ Mascitelli and P[ Passacantilli^ Synth[ Commun[\ 0889\ 19\
1454[ 81
89SC1572 A[ Bhattacharya\ J[ M[ Williams\ J[ S[ Amato\ U[ Dolling and E[ J[ J[ Grabowski^ Synth[
Commun[\ 0889\ 19\ 1572[ 020
89SC1872 B[ Contreras\ L[ Duhamel and G[ Ple^ Synth[ Commun[\ 0889\ 19\ 1872[ 52
89SC2952 Y[ Inoue\ K[ Ohuchi\ S[ Imaizumi and H[ Hagiwara^ Synth[ Commun[\ 0889\ 19\ 2952[ 133
89SC2958 K[ F[ Cheng and K[ P[ Chan^ Synth[ Commun[\ 0889\ 19\ 2958[ 298
89SC2974 D[ Brillon^ Synth[ Commun[\ 0889\ 19\ 2974[ 250
89SC2056 A[ Chesney and I[ E[ Marko^ Synth[ Commun[\ 0889\ 19\ 2056[ 33
89SC2148 M[ N[ Kanvinde\ S[ A[ Kulkarni and M[ V[ Paradkar^ Synth[ Commun[\ 0889\ 19\ 2148[ 182
89SC2154 E[ J[ Parish\ S[ Parish and H[ Honda^ Synth[ Commun[\ 0889\ 19\ 2154[ 023
89SC2248 E[ J[ Parish\ H[ Honda and D[ L[ Hileman^ Synth[ Commun[\ 0889\ 2248[ 004
89SL096 J[ C[ Anderson and S[ C[ Smith^ Synlett\ 0889\ 096[ 045
89SL006 D[ Crich and L[ B[ L[ Lim^ Synlett\ 0889\ 006[ 052
89SL044 M[ J[ Calverley^ Synlett\ 0889\ 044[ 28
89SL134 Y[ Ito and M[ Murakami^ Synlett\ 0889\ 134[ 307
89SL171 B[ Lygo and N[ O|Connor^ Synlett\ 0889\ 171[ 060
89SL234 I[ E[ Marko\ A[ Mekhal_a and W[ D[ Ollis^ Synlett\ 0889\ 234[ 183
89SL254 R[ M[ Moriarty\ R[ K[ Vaid and G[ F[ Koser^ Synlett\ 0889\ 254[ 052\ 067
89SL366 A[ Sera\ H[ Yamauchi\ H[ Yamada and K[ Itoh^ Synlett\ 0889\ 366[ 315
89SL592 J[ E[ Baldwin and I[ A[ O|Neil^ Synlett[\ 0889\ 592[ 585\ 602
89SL508 D[ S[ Brown\ M[ J[ Earle\ R[ A[ Fairhurst\ H[ Heaney\ G[ Papageorgiou\ R[ F[ Wilkins and
S[ C[ Eyley^ Synlett\ 0889\ 508[ 075
89SL530 M[ Frank!Neumann\ P[ Chemla and D[ Martina^ Synlett\ 0889\ 530[ 29
89SL614 D[ Enders and A[ Plant^ Synlett\ 0889\ 614[ 07\ 023
89SL624 R[ F[ W[ Jackson\ A[ Wood and M[ J[ Wythes^ Synlett\ 0889\ 624[ 029\ 523
89SUL72 A[ Senning^ Sulfur Letters\ 0889\ 00\ 72[ 269
89T868 J[ Brussee\ W[ T[ Loos\ C[ G[ Kruse and A[ Van der Gen^ Tetrahedron\ 0889\ 35\ 868[ 517
89T876 A[ R[ Katritzky and P[ A[ Harris^ Tetrahedron\ 0889\ 35\ 876[ 075\ 076
89T0680 M[ Tramontini and L[ Angiolini^ Tetrahedron\ 0889\ 35\ 0680[ 073
89T1024 D[ Crich\ K[ A[ Eustace\ S[ M[ Fortt and T[ J[ Ritchie^ Tetrahedron\ 0889\ 35\ 1024[ 181
89T1194 M[ Novi\ G[ Garbarino\ G[ Petrillo and C[ Dell|Erba^ Tetrahedron\ 0889\ 35\ 1194[ 553\ 556
89T2738 H[ Vorbruggen\ B[ D[ Bohn and K[ Krolikiewicz^ Tetrahedron\ 0889\ 35\ 2738[ 313
89T3938 J[ Miittendorf\ H[ Hiemstra and W[ N[ Speckamp^ Tetrahedron\ 0889\ 35\ 3938[ 311
89T3150 H[ Suga and M[ Schlosser^ Tetrahedron\ 0889\ 35\ 3150[ 16
89T3306 S[ Agarwal\ H[ P[ Tiwari and J[ P[ Sharma^ Tetrahedron\ 0889\ 35\ 3306[ 3\ 004
89T4102 Y[ Bessard\ U[ Muller and M[ Schlosser^ Tetrahedron\ 0889\ 35\ 4102[ 384
89T5240 H[ Muratake\ H[ Kumagami and M[ Natsume^ Tetrahedron\ 0889\ 35\ 5240[ 585
89T5490 C[ J[ Moody and R[ J[ Taylor^ Tetrahedron Lett[\ 0889\ 35\ 5490[ 055
89T5512 T[ P[ Kogan\ T[ C[ Somers and M[ C[ Venuti^ Tetrahedron\ 0889\ 35\ 5512[ 209
89T5758 H[ Firouzabadi\ M[ Seddighi\ E[ Mottaghinejad and M[ Bolourchian^ Tetrahedron\ 0889\
35\ 5758[ 4
89T6064 K[ Afarinkia\ C[ W[ Rees and J[ I[ G[ Cadogan^ Tetrahedron\ 0889\ 35\ 6064[ 49
89T6230 P[ E[ O|Bannon and W[ P[ Dailey^ Tetrahedron\ 0889\ 35\ 6230[ 379
89T6302 J[ R[ Hwu and S[ C[ Tsay^ Tetrahedron\ 0889\ 35\ 6302[ 315
89T6360 K[ Nakamura\ T[ Kitayama\ Y[ Inoue and A[ Ohno^ Tetrahedron\ 0889\ 35\ 6360[ 050
89T6458 M[ Miyashita\ B[ Z[ E[ Awen and A[ Yoshikoshi^ Tetrahedron\ 0889\ 35\ 6458[ 324
89T6488 R[ B[ Woodward\ W[ A[ Ayer\ J[ M[ Beaton et al^ Tetrahedron\ 0889\ 35\ 6488[ 230
89T7156 M[ North and G[ Pattenden^ Tetrahedron\ 0889\ 35\ 7156[ 507\ 508
89TL52 D[ Gravel\ L[ Farmer and C[ Ayotte^ Tetrahedron Lett[\ 0889\ 20\ 52[ 26
89TL068 T[ B[ Patrick\ S[ Hosseini and S[ Bains^ Tetrahedron Lett[\ 0889\ 20\ 068[ 16
89TL154 K[ Takeda\ K[ Torii and H[ Ogura^ Tetrahedron Lett[\ 0889\ 20\ 154[ 034
89TL212 M[ B[ Power and A[ R[ Barron^ Tetrahedron Lett[\ 0889\ 20\ 212[ 016
89TL884 C[ W[ Je}ord\ Q[ Tang and J[ Boukouvalas^ Tetrahedron Lett[\ 0889\ 20\ 884[ 296
89TL0138 F[ E}enberger\ B[ Horsch\ S[ Forster and T[ Ziegler^ Tetrahedron Lett[\ 0889\ 20\ 0138[ 517
89TL0254 H[ Vicente\ I[ N[ Rezzano and K[ M[ Smith^ Tetrahedron Lett[\ 0889\ 20\ 0254[ 53
89TL0318 M[ Thiam and F[ Chastrette^ Tetrahedron Lett[\ 0889\ 20\ 0318[ 30
89TL0722 C[ Retherford\ T[!S[ Chou\ R[ M[ Schelkun and P[ Knochel^ Tetrahedron Lett[\ 0889\ 20\
0722[ 190
89TL0866 S[ P[ Tanis\ M[ C[ McMills\ T[ A[ Scahill and D[ A[ Kloosterman^ Tetrahedron Lett[\ 0889\
20\ 0866[ 291
89TL1936 J[ E[ Baldwin and I[ A[ O|Neil^ Tetrahedron Lett[\ 0889\ 20\ 1936[ 585\ 693
89TL1940 J[ E[ Baldwin\ D[ J[ Aldous and I[ A[ O|Neil^ Tetrahedron Lett[\ 0889\ 20\ 1940[ 602
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80T864 C[ N[ Eid\ Jr[ and J[ P[ Konopelski^ Tetrahedron\ 0880\ 36\ 864[ 059
80T0098 R[ V[ Ho}man^ Tetrahedron\ 0880\ 36\ 0098[ 052
80T0654 J[ A[ Adams and D[ M[ Spero^ Tetrahedron\ 0880\ 36\ 0654[ 018
80T1572 A[ R[ Katritzky\ S[ Rachwal and G[ J[ Hitchings^ Tetrahedron\ 0880\ 36\ 1572[ 31
80T2196 J[ P[ Begue and D[ Bonnet!Delpon^ Tetrahedron\ 0880\ 36\ 2196[ 037
80T2236 J[ Viala\ P[ Munier and M[ Santelli^ Tetrahedron\ 0880\ 36\ 2236[ 084
80T2642 U[ Hedtmann\ R[ Klintz\ K[ Hobert\ J[ Frelek\ I[ Vlahov and P[ Welzel^ Tetrahedron\ 0880\
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80T3816 A[ C[ Gaumont\ L[ Wazneh and J[ M[ Denis^ Tetrahedron\ 0880\ 36\ 3816[ 226\ 240
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80T6602 C[ Bernaus\ J[ Font and P[ de March^ Tetrahedron\ 0880\ 36\ 6602[ 204
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81SC0856 W[ P[ Gri.th\ J[ M[ Jolli}e\ S[ V[ Ley\ K[ F[ Springhorn and P[ D[ Ti.n^ Synth[ Commun\
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81SC0882 J[ Muzart and A[ N[ Ajjou^ Synth[ Commun[\ 0881\ 11\ 0882[ 183
81SC1118 B[ Mauze and L[ Miginiac^ Synth[ Commun[\ 0881\ 11\ 1118[ 528
81SC1314 J[ G[ Lee\ K[ H[ Kwak and J[ P[ Hwang^ Synth[ Commun[\ 0811\ 11\ 1314[ 07\ 023
81SC1476 C[ Narayana\ N[ K[ Reddy and G[ W[ Kabalka^ Synth[ Commun[\ 0881\ 11\ 1476[ 022
81SL53 R[ Ballini\ G[ Bartoli\ R[ Castagnani\ E[ Marcantoni and M[ Petrini^ Synlett\ 0881\ 53[ 089
81SL66 G[ K[ Cheung\ I[ M[ Downie\ M[ J[ Earle\ H[ Heaney\ M[ F[ S[ Matough\ K[ F[ Shuhaibar
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81SL164 I[ E[ Marko and A[ Chesney^ Synlett\ 0881\ 164[ 33
81SL344 T[ Satoh and K[ Yamakawa^ Synlett[\ 0881\ 344[ 25\ 33\ 051\ 056\ 057\ 072
81SL372 A[ J[ Bennett\ J[ M[ Percy and M[ H[ Rock^ Synlett\ 0881\ 372[ 049
81SL380 M[ R[ Shipton^ Synlett\ 0881\ 380[ 067
81SL552 M[ Hayashi\ M[ Tamura and N[ Oguni^ Synlett\ 0881\ 552[ 521
81SL792 A[ Degl|Innocenti\ A[ Mordini\ S[ Pecchi\ D[ Pinzani\ G[ Reginato and A[ Ricci^ Synlett[\
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81SL898 J[!B[ Baudin\ M[!G[ Commenil\ S[ A[ Julia and Y[ Wang^ Synlett[\ 0881\ 898[ 258
81T0928 H[ N[ C[ Wong\ C[ R[ Niu\ Z[ Yang\ P[ M[ Hon\ H[ M[ Chang and C[ M[ Lee^ Tetrahedron\
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81T0188 L[ Longobardo\ G[ Mobbili\ E[ Tagliavini\ C[ Trombini and A[ Umani!Ronchi^ Tetrahedron\
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Copyright # 1995, Elsevier Ltd. All R ights Reserved Comprehensive Organic Functional Group Transformations