Reactions of Alkenes
Chapter 6
6-2
Characteristic Reactions
React ion
C C
HCl ( HX) H2 O
C C
C C
Br2 ( X2 ) Br2 ( X2 ) H2 O
H Hydrochlorin ation C C Cl (X) (hydrohalogen ation ) H Hydration C C OH (X) Br Bromin ation C C Br (X) (h alogenation) HO C C Br (X) Bromo(halo)hydrin formation
C C
6-3
Characteristic Reactions
C C
+ Hg(OAc) 2
H2 O
C C
BH3
C C
OsO4
C C
H2
6-4
Reaction Mechanisms
A
6-5
free energy change, DG0: a thermodynamic function relating enthalpy, entropy, and temperature DG0 = DH0 TDS0
exergonic reaction: a reaction in which the Gibbs free energy of the products is lower than that of the reactants; the position of equilibrium for an exergonic reaction favors products endergonic reaction: a reaction in which the Gibbs free energy of the products is higher than that of the reactants; the position of equilibrium for an endergonic reaction favors starting materials
6-6
summary of the relationships between DG0, DH0, DS0, and the position of chemical equilibrium
DS0 < 0 DG 0 > 0; th e position of equilib riu m favors reactants DS0 > 0 At h igh er temperatures w hen TDS0 > DH0 an d DG 0 < 0, th e position of equ ilibrium favors products DG 0 < 0; th e position of equilib riu m favors products
DH 0 > 0
DH 0 < 0
At low er temp eratu res w hen TDS0 < DH0 an d DG 0 < 0, th e position of equ ilibrium favors products
6-7
Energy Diagrams
Enthalpy
change, DH0: the difference in total bond energy between reactants and products
a measure of bond making (exothermic) and bond breaking (endothermic)
Heat
Energy Diagrams
Energy
diagram: a graph showing the changes in energy that occur during a chemical reaction Reaction coordinate: a measure in the change in positions of atoms during a reaction
Energy
Reaction coordinate
6-9
Activation Energy
Transition
state:
an unstable species of maximum energy formed during the course of a reaction a maximum on an energy diagram
Activation
Energy, DG: the difference in Gibbs free energy between reactants and a transition state
if DG is large, few collisions occur with sufficient energy to reach the transition state; reaction is slow if DG is small, many collisions occur with sufficient energy to reach the transition state; reaction is fast
6-10
Energy Diagram
a one-step reaction with no intermediate
6-11
Energy Diagram
A
6-12
How it is done
design experiments to reveal details of a particular chemical reaction propose a set or sets of steps that might account for the overall transformation a mechanism becomes established when it is shown to be consistent with every test that can be devised this does mean that the mechanism is correct, only that it is the best explanation we are able to devise
6-13
Why Mechanisms?
they are the framework within which to organize descriptive chemistry they provide an intellectual satisfaction derived from constructing models that accurately reflect the behavior of chemical systems they are tools with which to search for new information and new understanding
6-14
Electrophilic Additions
hydrohalogenation using HCl, HBr, HI hydration using H2O in the presence of H2SO4 halogenation using Cl2, Br2 halohydrination using HOCl, HOBr oxymercuration using Hg(OAc)2, H2O followed by reduction
6-15
Addition of HX
Carried
Addition
is regioselective
regioselective reaction: an addition or substitution reaction in which one of two or more possible products is formed in preference to all others that might be formed Markovnikovs rule: in the addition of HX, H2O, or ROH to an alkene, H adds to the carbon of the double bond having the greater number of hydrogens
6-16
HBr + 2-Butene
A two-step mechanism Step 1: proton transfer from HBr to the alkene gives a carbocation intermediate slow , rate H determining CH3 CH=CHCH3 + H Br CH3 CH-CHCH3 + Br s ec-Butyl cation (a 2 carbocation intermediate)
Step 2: reaction of the sec-butyl cation (an electrophile) with bromide ion (a nucleophile) completes the reaction
+ CH3 CHCH2 CH3 Br Bromide ion sec-Butyl cation (a nu cleophile) (an electrophile) fast Br CH3 CHCH2 CH3 2-Bromobu tane
6-17
HBr + 2-Butene
An
6-18
Carbocations
Carbocation: a species in which a carbon atom has only six electrons in its valence shell and bears positive charge Carbocations are classified as 1, 2, or 3 depending on the number of carbons bonded to the carbon bearing the positive charge electrophiles; that is, they are electron-loving Lewis acids
6-19
Carbocations
bond angles about a positively charged carbon are approximately 120 carbon uses sp2 hybrid orbitals to form sigma bonds to the three attached groups the unhybridized 2p orbital lies perpendicular to the sigma bond framework and contains no electrons
6-20
Carbocation Stability
a 3 carbocation is more stable than a 2 carbocation, and requires a lower activation energy for its formation a 2 carbocation is, in turn, more stable than a 1 carbocation, methyl and 1 carbocations are so unstable that they are never observed in solution
6-21
Carbocation Stability
relative stability
H H C+ H CH3 C+ H Ethyl cation (1) CH3 CH3 C+ H Isopropyl cation (2) CH3 CH3 C+ CH3 t ert-Bu tyl cation (3)
methyl and primary carbocations are so unstable that they are never observed in solution
6-22
Carbocation Stability
we can account for the relative stability of carbocations if we assume that alkyl groups bonded to the positively charged carbon are electron releasing and thereby delocalize the positive charge of the cation we account for this electron-releasing ability of alkyl groups by (1) the inductive effect, and (2) hyperconjugation
6-23
6-24
Hyperconjugation
involves partial overlap of the -bonding orbital of an adjacent C-H or C-C bond with the vacant 2p orbital of the cationic carbon the result is delocalization of the positive charge
6-25
Addition of H2O
addition of water is called hydration acid-catalyzed hydration of an alkene is regioselective; hydrogen adds preferentially to the less substituted carbon of the double bond HOH adds in accordance with Markovnikovs rule
CH3 CH=CH2 + H2 O Propene H2 SO4 OH H CH3 CH-CH2 2-Propanol
H2 SO4
6-26
Addition of H2O
Step 1: proton transfer from H3O+ to the alkene
+
CH3 CH= CH 2
H O H H
Step 2: reaction of the carbocation (an electrophile) with water (a nucleophile) gives an oxonium ion
+
:
+
CH3 CHCH 3
:O H H
A 2o carbocation intermediate
CH3 CHCH 3
: O- H H
fast
O+
6-27
Carbocation Rearrangements
In
electrophilic addition to alkenes, there is the possibility for rearrangement Rearrangement: a change in connectivity of the atoms in a product compared with the connectivity of the same atoms in the starting material
6-28
Carbocation Rearrangements
in addition of HCl to an alkene
Cl + HCl 3,3-D imethyl1-bu tene + Cl
2-Ch loro-3,3-dimethylbutan e 2-Chloro-2,3-dimethylbu tane (the exp ected p rodu ct; 17%) (the major p rodu ct; 83%)
6-29
Carbocation Rearrangements
the driving force is rearrangement of a less stable carbocation to a more stable one
CH3 CH3 CCH= CH2 + H H 3-Methyl-1-butene Cl : slow, rate determining CH3 C- CHCH3 + : Cl : CH3
the less stable 2 carbocation rearranges to a more stable 3 one by 1,2-shift of a hydride ion
CH3 CH3 C- CHCH3
+
: :
H A 2 carbocation intermediate
fast
Carbocation Rearrangements
reaction of the more stable carbocation (an electrophile) with chloride ion (a nucleophile) completes the reaction
C H 3 C- CH 2 CH 3 + : Cl : + CH 3
fast
CH 3 CH 3 C- C H 2 CH 3 : Cl : :
: :
2-Chloro-2-methylbutane
6-31
Br2
CH2 Cl2
Br +
Br2
CH2 Cl2
Cyclohexen e
addition occurs with anti stereoselectivity; halogen atoms add from the opposite face of the double bond we will discuss this selectivity in detail in Section 6.7
6-32
6-33
Br
Br C C Br
-
6-34
+ Br2
Br Br
Br
of an alkene with Br2 or Cl2 in water forms a halohydrin Halohydrin: a compound containing -OH and -X on adjacent carbons
CH3 CH=CH2 + Cl2 + H2 O Propene HO Cl CH3 CH-CH2 + HCl 1-Chloro-2-p ropanol (a ch loroh yd rin )
6-36
to account for the regioselectivity and the anti stereoselectivity, chemists propose the three-step mechanism in the next screen
6-37
: :
H - Br H
-
:Br :
H R
Step 2: attack of H2O on the more substituted carbon opens the three-membered ring
:
:Br : H O: H H R C C H H H H R C :Br : C H H
6-38
+
H
O H
As
the C-X bond to the more substituted carbon is longer than the one to the less substituted carbon because of this difference in bond lengths, the transition state for ring opening can be reached more easily by attack of the nucleophile at the more substituted carbon
6-39
6-40
Oxymercuration/Reduction
Oxymercuration
1-Pen tene
reduction
OH NaBH4 HgOAc H 2-Pen tanol OH O + CH COH + Hg 3 Acetic acid
6-41
Oxymercuration/Reduction
an important feature of oxymercuration/reduction is that it occurs without rearrangement
1 . Hg(OAc) 2 , H2 O 2 . NaBH4 3,3-D imeth yl-1-b utene
HgOAc
Cyclop entene
H H Cyclopen tanol
6-42
Oxymercuration/Reduction
Step 1: dissociation of mercury(II) acetate
6-43
Oxymercuration/Reduction
Step 3: regioselective attack of H2O (a nucleophile) on the bridged intermediate opens the three-membered ring
6-44
Oxymercuration/Reduction
Anti
stereoselective
we account for the stereoselectivity by formation of the bridged bromonium ion and anti attack of the nucleophile which opens the three-membered ring
Regioselective
of the two carbons of the mercurinium ion intermediate, the more substituted carbon has the greater degree of partial positive character alternatively, computer modeling indicates that the CHg bond to the more substituted carbon of the bridged intermediate is longer than the one to the less substituted carbon therefore, the ring-opening transition state is reached more easily by attack at the more substituted carbon
6-45
Hydroboration/Oxidation
Hydroboration:
Borane
6-46
Hydroboration/Oxidation
borane forms a stable complex with ethers such as THF the reagent is used most often as a commercially available solution of BH3 in THF
2
: O:
+ B2 H6
+ :O BH3 BH3 TH F
Tetrahydrofuran (THF)
6-47
Hydroboration/Oxidation
Hydroboration
is both
1-Methylcyclopentene
6-48
Hydroboration/Oxidation
concerted regioselective and syn stereoselective addition of B and H to the carbon-carbon double bond
H B H CH 3 CH 2 CH 2 CH= CH 2 B CH 3 CH 2 CH 2 CH-CH 2
trialkylboranes are rarely isolated oxidation with alkaline hydrogen peroxide gives an alcohol and sodium borate
R3 B + H2 O2 + NaOH A trialkylborane 3 ROH + Na3 BO3 An alcohol
6-49
Hydroboration/Oxidation
Hydrogen
step 1: hydroperoxide ion (a nucleophile) donates a pair of electrons to boron (an electrophile)
R + R B O-O-H R A trialk ylb orane Hydrop eroxide ion (an electroph ile) (a nu cleophile) R R B O O H R
step 2: rearrangement of an R group with its pair of bonding electrons to an adjacent oxygen atom
R R B O O H R R R B O R
O-H
6-50
Hydroboration/Oxidation
step 3: reaction of the trialkylborane with aqueous NaOH gives the alcohol and sodium borate
( RO) 3 B + 3 NaOH A trialkylborate 3 ROH + Na3 BO3 Sodiu m b orate
6-51
Oxidation/Reduction
Oxidation: Reduction: Recognize
alternatively, the loss of H, the gain of O, or both alternatively, the gain of H, the loss of O, or both 1. write a half-reaction showing one reactant and its product(s) 2. complete a material balance; use H2O and H+ in acid solution, use H2O and OH- in basic solution 3. complete a charge balance using electrons, e-
6-52
Oxidation/Reduction
three balanced half-reactions
CH3 CH= CH2 + H2 O Propene OH CH3 CHCH3 2-Propanol HO OH CH3 CH= CH2 + 2 H2 O Propene CH3 CH= CH2 + 2 H+ + 2 e Propene CH3 CHCH2 + 2 H+ + 2 e 1,2-Propane diol CH3 CH2 CH3 Propane
6-53
6-54
6-55
Oxidation with O3
Treatment
of an alkene with ozone followed by a weak reducing agent cleaves the C=C and forms two carbonyl groups in its place
CH3 CH3 C= CHCH2 CH 3 2-Methyl-2-pentene O
6-56
Oxidation with O3
the initial product is a molozonide which rearranges to an isomeric ozonide
CH 3 CH = CH CH 3 2-Butene O3 O OO C H 3 CH - C H CH 3 A molozonide H H3 C O H O C H 3 CH
C C ( CH 3 ) 2 S CH 3 O O Acetaldehyde An ozonide
6-57
Reduction of Alkenes
Most
alkenes react with H2 in the presence of a transition metal catalyst to give alkanes
+ H2 Cyclohexene Pd 25C, 3 atm Cyclohexane
commonly used catalysts are Pt, Pd, Ru, and Ni the process is called catalytic reduction or, alternatively, catalytic hydrogenation addition occurs with syn stereoselectivity
6-58
Reduction of Alkenes
Mechanism
of catalytic hydrogenation
6-59
Reduction of Alkenes
even though addition syn stereoselectivity, some product may appear to result from trans addition
CH3 CH3 1,2-D imethylcyclohexene H2 / Pt CH3
+
reversal of the reaction after the addition of the first hydrogen gives an isomeric alkene, etc.
CH3 CH3 1,2-D imeth ylcyclohexene H2 / Pt H CH3 H Pt H CH3 CH3 CH3 1,6-D imeth ylcyclohexene
6-60
DH0 of Hydrogenation
Reduction
DH0
DH0 for a trans alkene is lower than that of an isomeric cis alkene
a trans alkene is more stable than a cis alkene
6-61
DH0 of Hydrogenation
N ame Eth yle ne Prop en e 1-Bu te ne cis -2-Bu ten e t rans -2-Bu te ne 2-M eth yl-2-b uten e 2,3-D ime th yl-2-b ute n e S tru ctural Formu la CH2 =CH2 CH3 CH=CH2 DH [k J (k cal)/m ol] -137 (-32.8) -126 (-30.1) -127 (-30.3) -120 (-28.6) -115 (-27.6) -113 (-26.9) -111 (-26.6)
6-62
Reaction Stereochemistry
In
several of the reactions presented in this chapter, chiral centers are created Where one or more chiral centers are created, is the product
one enantiomer and, if so, which one? a pair of enantiomers as a racemic mixture? a meso compound? a mixture of stereoisomers?
As
we will see, the stereochemistry of the product for some reactions depends on the stereochemistry of the starting material; that is, some reactions are stereospecific
6-63
Reaction Stereochemistry
We
Br2
CH2 Cl2
two stereoisomers are possible for 2-butene; a pair of cis,trans isomers three stereoisomers are possible for the product; a pair of enantiomers and a meso compound if we start with the cis isomer, what is the stereochemistry of the product? if we start with the trans isomer, what is the stereochemistry of the product? 6-64
Bromination of cis-2-Butene
reaction of cis-2-butene with bromine forms bridged bromonium ions which are meso and identical
6-65
Bromination of cis-2-Butene
attack of bromide ion at carbons 2 and 3 occurs with equal probability to give enantiomeric products as a racemic mixture
6-66
Bromination of trans-2-Butene
reaction with bromine forms bridged bromonium ion intermediates which are enantiomers
6-67
Bromination of trans-2-Butene
attack of bromide ion in either carbon of either enantiomer gives meso-2,3-dibromobutane
6-68
Bromination of 2-Butene
Given
Stereospecific
reaction: a reaction in which the stereochemistry of the product depends on the stereochemistry of the starting material
6-69
Oxidation of 2-Butene
OsO4 oxidation of cis-2-butene gives meso-2,3butanediol
H3 C H H C H H3 C
2 3 2 3
OsO4 ROOH
HO OH (2S,3R)-2,3-Butanediol HO
2
OH C
3
H H3 C (2R,3S)-2,3-Butanediol
H CH3
6-70
Oxidation of 2-Butene
OsO4
oxidation of trans-2-butene gives the enantiomers of 2,3-butanediol as a racemic mixture (optically inactive)
H3 C H C H
2 3 2 3
CH3
OsO4 ROOH
HO OH (2S,3S)-2,3-Butaned iol HO
2
H3 C H trans-2-Buten e (achiral)
OH C
3
H H3 C (2R,3R)-2,3-Butaned iol
CH3 H
6-71
Reaction Stereochemistry
We
have seen two examples in which reaction of achiral starting materials gives chiral products
in each case, the product is formed as a racemic mixture (which is optically inactive) or as a meso compound (which is also optically inactive)
These
examples illustrate a very important point about the creation of chiral molecules
optically active (enantiomerically pure) products can never be produced from achiral starting materials and achiral reagents under achiral conditions although the molecules of product may be chiral, the product is always optically inactive (either meso or a pair of enantiomers)
6-72
Reaction Stereochemistry
Next
the presence of the bulky tert-butyl group controls the orientation of the two bromine atoms added to the ring
6-73
Reaction Stereochemistry
Finally,
PPh2 PPh2
6-74
Reaction Stereochemistry
treating (R)-BINAP with ruthenium(III) chloride forms a complex in which ruthenium is bound in the chiral environment of the larger BINAP molecule this complex is soluble in CH2Cl2 and can be used as a homogeneous hydrogenation catalyst
(R)-BINAP + RuCl3 (R)-BINAP-Ru
6-75
Reaction Stereochemistry
BINAP-Ru complexes are somewhat specific for the types of C=C they reduce to be reduced, the double bond must have some kind of a neighboring group that serves a directing group
(S)-BIN A P-Ru OH H2 OH
(S)-3,7-D imethyl-6-octen-1-ol
6-76
Reactions of Alkenes
End Chapter 6
6-77