Oxi dati on of Al cohol s (CH-OH !

C=O)

Reagent Name Product
w/1 OH
Comments
CrO
3
, H
2
SO
4
Jones CO
2
H rapid
strongly acidic conditions
CrO
3
, pyridine Collins
(Sarett)
CHO requires large excess of reagent, anh. cond.
Sarett: in situ generation in pyridine
Collins: isolated solid; rxn in DCM
Radcliffe: in situ generation in DCM
note: add CrO
3
to pyridine!! Strong exotherm
pyridinium
chlorochromate
PCC
(Corey-Suggs)
CHO can be used in near stoichiometric amounts
sensitive to sterics
3 allylic alcohols may rearrange
accelerated by addn of 4 MS
reagent slightly acidic - can buffer w/NaOAc
pyridinium
dichromate
PDC
(Corey-Schmidt)
CHO
(in CH
2
Cl
2
)
neutral, mild reaction conditions
axial alcohols oxidize faster than equatorial

CO
2
H
(in DMF)
conjugated alcohols give aldehyde
non-conjugated alcohols give acid
MnO
2
CHO selective oxidation of conjugated alcohols
requires large excess
mild; no double bond isomerization
MnO
2
, KCN,
MeOH
CO
2
Me oxidation of 1 conjugated alcohols to esters
KMnO
4
CO
2
H very powerful oxidant
over oxidation/side rxns a problem (H
+
/OH
-
)
for sensitive substrates: 5% NaH
2
PO
4
(pH 7)
BaMnO
4
CHO reactivity similar to MnO
2

RuO
4
CO
2
H very powerful, nonselective oxidant
oxidizes multiple bonds & 1,2-diols
highly toxic
tetra-n-propyl-
ammonium
perruthenate
TPAP CHO very mild
does not react with multiple bonds
catalytic Ru; use NMO reoxidant
(COCl)
2
, DMSO,
Et
3
N
Swern CHO mild conditions; commonly used
not sensitive to steric factors
many variations (TFAA, Ac
2
O, SOCl
2
, etc.)
DMS, NCS (Corey-Kim) CHO allylic & benzylic alcohols give chloride
DMSO, DCC Moffatt CHO mild conditions
3 alcohols may eliminate
SO
3
pyr Parikh-Doering CHO mild conditions
Reagent Name Product
w/1 OH
Comments
Ag
2
CO
3
, celite Fetizons
reagent
CHO mild, neutral conditions
$$$; must use large excess
useful for substrates prone to rearrangement
or racimization
1,3- and 1,4-diols are oxidized to lactones
(1 alcohols oxidized faster than 2)
Ag
2
O --- CHO oxidized to CO
2
H in presence of alcohol
best choice for oxidation of saturated CHO
Dess-Martin
periodinane
Dess-Martin CHO mild reagent; near neutral conditions
can be used in presence of sensitive FG
will not oxidize N or S functions
IBX

CHO one step formation of ",#-unsaturated
carbonyls from saturated alcohols
mild reagent for oxidation of 1,2-diols
Al(OiPr0)
3
,
acetone
Oppenauer --- mild
does not work well with 1 alcohols
NaOCl

CHO selective oxidation of 2 alcohols in presence
of 1 alcohols
NaClO
2
Pinnick --- mild, inexpensive
CHO oxidized to CO
2
H in presence of alcohol
good for unsaturated aldehyde oxidation
TEMPO CHO will not oxidize amines




References
Chromium Based Reagents
Comp. Org. Syn. 1991, vol 7, 251; Org. React. 1998, 53, 1. (general review)
J. Chem. Soc. 1946, 39; Org. Syn. Coll. Vol. V, 310. (Jones)
Tetrahedron Lett. 1968, 3363; J. Org. Chem. 1970, 35, 644. (Collins/Radcliffe)
J. Am. Chem. Soc. 1953, 75, 422. (Sarett)
Tetrahedron Lett. 1975, 2647. (PCC)
Tetrahedron Lett. 1979, 20, 399. (PDC)

Manganese Based Reagents
Synthesis 1976, 65 and 133. (MnO
2
)
Acc. Chem. Res. 2005, 38, 851. (MnO
2
)
J. Am. Chem. Soc. 1968, 90, 5616 and 5618. (MnO
2
, KCN, MeOH)
Synthesis 1976, 85. (KMnO
4
and BaMnO
4
)
Tetrahedron Lett. 1986, 27, 4537. (KMnO
4
- buffered)

Ruthenium Based Reagents
J. Am. Chem. Soc. 1953, 75, 3838; J. Org. Chem. 1981, 46, 3936. (RuO
4
)
Aldrichimica Acta 1990, 23, 13; Synthesis 1994, 639. (TPAP)

DMSO Based Reagents
Synthesis 1990, 857. (general review)
Org. React. 1990, 34, 297. (general review)
J. Org. Chem. 1976, 41, 3329. (Swern)
J. Am. Chem. Soc. 1972, 94, 7586; Tetrahedron Lett. 1974, 287. (Corey-Kim)
J. Am. Chem. Soc. 1963, 85, 3027. (Moffatt)
J. Am. Chem. Soc. 1967, 89, 5505. (Parikh-Doering)
Org. React. 1991, 40, 157; Synthesis 1997, 1353. (Pummerer)

Silver Based Reagents
J. Chem. Soc., Chem. Commun. 1969, 1102; Synthesis 1979, 401. (Fetizons reagent)
J. Chem. Soc. 1946, 39; Org. Syn. Coll. Vol. V, 310. (Jones)
Org. Syn., Coll Vol. IV, 1963, 972. (Ag
2
O)

Other Reagents
J. Am. Chem. Soc. 1983, 48, 4155; J. Org. Chem. 1993, 58, 2899; J. Org. Chem. 1994, 59, 7549.
(Dess-Martin)
J. Am. Chem. Soc. 2000, 122, 7596. (IBX)
Synthesis 1994, 1007. (Oppenauer)
Tetrahedron Lett. 1982, 23, 4647. (NaOCl)
Acta. Chem. Scand. 1973, 27, 888; J. Org. Chem. 1980, 45, 4825; Tetrahedron 1981, 37, 2091.
(Pinnick)
Synthesis 1996, 1153. (TEMPO)