Organic

Chemistry
William H. Brown
Christopher S. Foote
Brent L. Iverson
6-1

Reactions
of Alkenes
Chapter 6

6-2

Characteristic Reactions
Descriptive Name(s )

Rea c t io n

C C

HCl
(HX)

C C

H2O

C C

Br2
(X2 )

C C

Br2
(X2 )

H
C C
Cl (X)
H
C C
OH
(X)Br
C C
Br (X)
H2 O

Hydrochlorination
(hydrohalogenation)
Hydration

Bromination
(halogenation)

HO
Bromo(halo)hydrin
C C
Br (X) formation

6-3

Characteristic Reactions
C C

+ Hg(OAc) 2

C C

C C

+ OsO
4

C C

BH3

H2

H2 O

HgOAc
Oxymercuration
C C
HO
C C
H BH2

Hydroboration

C C
HO OH

Diol formation
(oxidation)

C C
H H

Hydrogenation
(reduction)

6-4

Reaction Mechanisms

A reaction mechanism describes how a reaction

occurs
which bonds are broken and which new ones are
formed
the order and relative rates of the various bondbreaking and bond-forming steps
if in solution, the role of the solvent
if there is a catalyst, the role of a catalyst
the position of all atoms and energy of the entire
system during the reaction

6-5

Gibbs Free Energy

Gibbs free energy change, G0: a thermodynamic

function relating enthalpy, entropy, and
temperature
G0 = H0 TS0

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

Gibbs Free Energy

a change in Gibbs free energy is directly related to
chemical equilibrium
0
G = -RT ln Keq
summary of the relationships between G0, H0, S0,
and the position of chemical equilibrium

At higher temperatures
when T

6-7

Energy Diagrams

Enthalpy change, : the difference in total

bond energy between reactants and products
a measure of bond making (exothermic) and bond
breaking (endothermic)

Heat of reaction, : the difference in enthalpy

between reactants and products
exothermic reaction: a reaction in which the enthalpy
of the products is lower than that of the reactants; a
reaction in which heat is released
endothermic reaction:
reaction a reaction in which the enthalpy
of the products is higher than that of the reactants; a
reaction in which heat is absorbed
6-8

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, G: the difference in Gibbs

free energy between reactants and a transition
state
if G is large, few collisions occur with sufficient
energy to reach the transition state; reaction is slow
if G 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 two-step reaction with one intermediate

6-12

Developing a Reaction Mechanism

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 out with pure reagents or in a polar

solvent such as acetic acid
Br H

CH3 CH=CH2
Propene

+ HBr

H Br

CH3 CH-CH2 + CH3 CH-CH2

2-Bromopropane 1-Bromopropane
(not observed)

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
sec-Butyl cation
(a 2 carbocation
intermediate)
Step 2: reaction of the sec-butyl cation (an electrophile) with
bromide ion (a nucleophile) completes the reaction
+ CH3CHCH2 CH3
Br
Bromide ion sec-Butyl cation
(a nucleophile) (an electrophile)

fast

Br
CH3CHCH2 CH3
2-Bromobutane

6-17

HBr + 2-Butene

An energy diagram for the two-step addition of

HBr to 2-butene
the reaction is exergonic

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
Methyl
cation
(methyl)

CH3

H
C+

H
Ethyl
cation
(1)

CH3

CH3
C+

H
Isopropyl
cation
(2)

CH3

CH3
C+

CH3
tert-Butyl
cation
(3)

Increasing carbocation stability

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

The Inductive Effect

the positively charged carbon polarizes electrons of

adjacent sigma bonds toward it
the positive charge on the cation is thus localized over
nearby atoms
the larger the volume over which the positive charge is
delocalized, the greater the stability of the cation

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
CH3CH=CH2 + H2O
Propene

CH3

CH3C=CH2 + H2O
2-Methylpropene

H2SO4

OH H
CH3CH-CH2
2-Propanol

CH3
CH3C-CH2
HO H
2-Methyl-2-propanol

H2SO4

6-26

Addition of H2O
Step 1: proton transfer from H3O+ to the alkene
H O H
H

CH3 CHCH3

CH3 CH=CH2

slow, rate
determining

:O H

A 2o carbocation H
intermediate

CH3 CHCH3

CH3 CHCH3

O+

:O-H

H
H
An oxonium ion

Step 3:

Step 2: reaction of the carbocation (an electrophile)

with water
+ (a nucleophile) gives an oxonium ion
fast

: +
fast
CH
CHCH
proton3 transfer
to water
CH3gives
CHCHthe
3
H O H
3 + alcohol

H :
O:
H

+
O
:
H
H

:OH
:

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-Dimethyl1-butene

Cl

2-Chloro-3,3-dimethylbutane 2-Chloro-2,3-dimethylbutane
(the expected product; 17%)
(the major product; 83%)

of an alkeneOH
in acid-catalyzed hydration
H2 SO
4
+

3-Methyl-1-butene

H2 O

2-Methyl-2-butanol

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

slow, rate
CH3
: :
determining
CH3 C-CHCH3 + :Cl
Cl
: :
: :
+
H
A 2 carbocation
intermediate

the less stable 2 carbocation rearranges to a more

stable 3 one
ion
CHby 1,2-shift of a hydride
CH
3

CH3 C-CHCH3
+

fast

CH3 C-CHCH3
+

H
A 3 carbocation
6-30

Carbocation Rearrangements
reaction of the more stable carbocation (an
electrophile) with chloride ion (a nucleophile)
completes the reaction
CH3

CH3 C- CH2 CH3 + :Cl :

+

fast

CH3

CH3 C-CH2 CH3

:Cl :

2-Chloro-2-methylbutane

6-31

Addition of Cl2 and Br2

carried out with either the pure reagents or in an inert
solvent such as CH2Cl2
CH3 CH=CHCH3
2-Butene

Br2

CH2Cl2

Br Br
CH3CH-CHCH3
2,3-Dibromobutane

addition of bromine or chlorine to a cycloalkene gives a

trans-dihalocycloalkane
+

Br2

Cyclohexene

Br
CH2 Cl2

Br

Br
Br
trans-1,2-Dibromocyclohexane
(a racemic mixture)

addition occurs with anti stereoselectivity;

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

Addition of Cl2 and Br2

Step 1: formation of a bridged bromonium ion
intermediate
Br
Br
C

Br

Br
C

Br
C

These carbocations are major

contributing structures

+ Br

The bridged bromonium

ion retains the geometry

6-33

Addition of Cl2 and Br2

Step 2: attack of halide ion (a nucleophile) from the
opposite side of the bromonium ion (an electrophile)
opens the three-membered ring to give the product
Br

Br
C

Br
Br

Anti (coplanar) orientation

of added bromine atoms

C
Br

Br
Newman projection
of the product
Br

Br

Br

Br

C
Br

Anti (coplanar) orientation

of added bromine atoms

Br
Newman projection
of the product

6-34

Addition of Cl2 and Br2

for a cyclohexene, anti coplanar addition corresponds
to trans diaxial addition
the initial trans diaxial conformation is in equilibrium
with the more stable trans diequatorial conformation
because the bromonium ion can form on either face of
the alkene with equal probability, both trans
enantiomers are formed as a racemic mixture
Br

+ Br2

Br

Br

Br
(1S,2S)-1,2-Dibromocyclohexane

Br

Br

Br
Br
(1R,2R)-1,2-Dibromocyclohexane
6-35

Addition of HOCl and HOBr

Treatment of an alkene with Br2 or Cl2 in water

forms a halohydrin
Halohydrin: a compound containing -OH and -X
on adjacent carbons
CH3CH=CH2 + Cl2 + H2O
Propene

HO Cl
CH3CH-CH2

+ HCl

1-Chloro-2-propanol
(a chlorohydrin)

6-36

Addition of HOCl and HOBr

reaction is both regiospecific (OH adds to the more
substituted carbon) and anti stereoselective
both selectivities are illustrated by the addition of
HOBr to 1-methylcyclopentene
Br2/ H2O

OH
Br

1-Methylcyclopentene

OH
Br

+ HBr

H
H
2-Bromo-1-methylcyclopentanol
( a racemic mixture )

to account for the regioselectivity and the anti

stereoselectivity, chemists propose the three-step
mechanism in the next screen

6-37

Addition of HOCl and HOBr

Step 1: formation
of a bridged halonium ion intermediate
:
: Br :

: Br
: :
H
R

H -Br
H

:
: Br :

: Br:

C
C
H
H
R
H
bridged bromonium
ion

H
H
R
H
minor contributing
structure

Step 2: attack of H2O on the more substituted carbon

opens the three-membered ring
: Br:
:
H O:
H

H
R

H
R
H
H

+
H

O
:

:
: Br :

C
H

C
H

H
6-38

Addition of HOCl and HOBr

Step 3: proton transfer to H2O completes the reaction
H
R

+
H

H
R

Br
C
H

C
H

O H

Br
C

C
H

+ H3 O+

As the elpot map on the next screen shows

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

Addition of HOCl and HOBr

bridged bromonium ion from propene

6-40

Oxymercuration/Reduction

Oxymercuration followed by reduction results in

hydration of a carbon-carbon double bond
oxymercuration

OH

+ Hg(OAc) 2 + H2O
1-Pentene

HgOAc
An organomercury
compound

Mercury(II)
acetate

reductionOH
HgOAc

O
+ CH3COH

NaBH4

OH
H
2-Pentanol

Acetic
acid

O
+ CH3COH + Hg
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

OH
3,3-Dimethyl-2-butanol

3,3-Dimethyl-1-butene

stereoselectivity
oxymercuration occurs with anti NaBH
H

Cyclopentene

Hg(OAc) 2
H2O

OH

H
HgOAc
(Anti addition of
OH and HgOAc)

OH

H
H
Cyclopentanol

6-42

Oxymercuration/Reduction
Step 1: dissociation of mercury(II) acetate

Step 2: formation of a bridged mercurinium ion

intermediate; a two-atom three-center bond

6-43

Oxymercuration/Reduction
Step 3: regioselective attack of H2O (a nucleophile) on
the bridged intermediate opens the three-membered
ring

Step 4: reduction of the C-HgOAc bond

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: the addition of borane, BH3, to an

alkene to form a trialkylborane
H

CH2 CH3

H B

+ 3CH2 =CH2

H
Borane

CH3 CH2 B
CH2 CH3
Triethylborane
(a trialkylborane)

Borane dimerizes to diborane, B2H6

2BH3
Borane

B2 H6
Diborane

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:

+ B 2 H6

Tetrahydrofuran
(THF)

+ : O BH3
BH3 THF

6-47

Hydroboration/Oxidation

Hydroboration is both
regioselective (boron to the less hindered carbon)
and syn stereoselective
+
H

CH3

1-Methylcyclopentene

BH3

H
BR2

H3 C
H

(Syn addition of3)BH

(R = 2-methylcyclopentyl)

6-48

Hydroboration/Oxidation
concerted regioselective and syn stereoselective
addition of B and H to the carbon-carbon double bond

H B
H
CH3 CH2 CH2 CH=CH2

CH3 CH2 CH2 CH-CH2

trialkylboranes are rarely isolated

oxidation with alkaline hydrogen peroxide gives an
alcohol
and+sodium
R B
H O + borate
3ROH + Na BO
NaOH
3

A trialkylborane

An alcohol

6-49

Hydroboration/Oxidation

Hydrogen peroxide oxidation of a trialkylborane

step 1: hydroperoxide ion (a nucleophile) donates a
pair of electrons to boron (an electrophile)
R
+
R B
O-O-H
R
A trialkylborane Hydroperoxide ion
(an electrophile) (a nucleophile)

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
R B O O H
R

R B O

+ O-H

6-50

Hydroboration/Oxidation
step 3: reaction of the trialkylborane with aqueous
NaOH gives the alcohol and sodium borate
+ 3NaOH
A trialkylborate
(RO)3 B

3ROH + Na3 BO3

Sodium borate

6-51

Oxidation/Reduction

Oxidation: the loss of electrons

alternatively, the loss of H, the gain of O, or both

Reduction: the gain of electrons

alternatively, the gain of H, the loss of O, or both

Recognize using a balanced half-reaction

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
CH3 CH= CH2 + 2 H2 O
Propene
CH3 CH= CH2 + 2 H+ + 2 e Propene

OH
CH3 CHCH3
2-Propanol
HO OH
CH3 CHCH2 + 2 H+ + 2 e 1,2-Propanediol
CH3 CH2 CH3
Propane

6-53

Oxidation with OsO4

OsO4 oxidizes an alkene to a glycol,

glycol a compound
with OH groups on adjacent carbons
oxidation is syn stereoselective
OsO4

O O
Os
O O
A cyclic osmate

NaHSO3
H2O

OH

OH
cis-1,2-Cyclopentanediol
(a cis glycol)

6-54

Oxidation with OsO4

OsO4 is both expensive and highly toxic
it is used in catalytic amounts with another oxidizing
agent to reoxidize its reduced forms and, thus, recycle
OsO4
HOOH
Hydrogen
peroxide

CH3
CH3 COOH
CH3
tert-Butyl hydroperoxide
(t-BuOOH)

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

O
+ HCCH2 CH3

1. O3
CH3 CCH3
2. (CH3 ) 2 S
2-Methyl-2-pentene
Propanone
Propanal
(a ketone) (an aldehyde)

CH3 C=CHCH2 CH3

6-56

Oxidation with O3
the initial product is a molozonide which rearranges to
an isomeric ozonide
CH3 CH=CHCH3
2-Butene

O3

O OO
CH3 CH-CHCH3
A molozonide
H

O
CH3 CH

C
C
(CH3 ) 2 S
CH3
O O
Acetaldehyde
An ozonide

H3 C

6-57

Reduction of Alkenes

Most alkenes react with H2 in the presence of a

transition metal catalyst to give alkanes
+

H
2

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

H2 / Pt

CH3
1,2-Dimethylcyclohexene

CH3
+

CH3
70% to 85%
cis-1,2-Dimethylcyclohexane

CH3
30% to15%
trans-1,2-Dimethylcyclohexane
(racemic)

reversal of the reaction after the addition of the first

CH3
hydrogen CH
gives
an
isomeric
alkene, etc.
CH3
3
H2/ Pt

CH3
1,2-Dimethylcyclohexene

H
Pt
HCH3

CH3
1,6-Dimethylcyclohexene

6-60

 H0 of Hydrogenation

Reduction of an alkene to an alkane is

exothermic
there is net conversion of one pi bond to one sigma
bond

H0 depends on the degree of substitution

the greater the substitution, the lower the value of H

H0 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

 H0 of Hydrogenation
Name

Structural
Formula
CH2 =CH 2
CH3 CH=CH2

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 saw in Section 6.3D that bromine adds to 2butene to give 2,3-dibromobutane

CH3 CH=CHCH3
2-Butene

Br2

CH2Cl2

Br Br
CH3CH-CHCH3
2,3-Dibromobutane

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 these results, we say that addition of Br2 or

Cl2 to an alkene is stereospecific
bromination of cis-2-butene gives the enantiomers of
2,3-dibromobutane as a racemic mixture
bromination of trans-2-butene gives meso-2,3dibromobutane

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
H
H

H3C

C
H
H3 C

CH3
cis-2-Butene
(achiral)

OsO4

CH3

HO
OH
(2S,3R)-2,3-Butanediol

ROOH
HO

OH
2

identical;
a meso
compound

H
H
CH3
H3 C
(2R,3S)-2,3-Butanediol

6-70

Oxidation of 2-Butene

OsO4 oxidation of an alkene is stereospecific

oxidation of trans-2-butene gives the enantiomers of 2,3butanediol as a racemic mixture (optically inactive)
H3 C

H
2

C
H

CH3

H3 C
H
trans-2-Butene
(achiral)

OsO4

CH3
H

HO
OH
(2S,3S)-2,3-Butanediol

ROOH
HO

OH

a pair of
enantiomers;
a racemic
mixture

CH3
H

H
H3 C
(2R,3R)-2,3-Butanediol

and oxidation of cis-2-butene gives meso 2,3-butanediol (also

optically inactive)

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)

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Reaction Stereochemistry

Next let us consider the reaction of a chiral

starting material in an achiral environment
the bromination of (R)-4-tert-butylcyclohexene
only a single diastereomer is formed
Br2
(R)-4-tert-Butylcyclohexene

Br
Br

redraw as
a chair
conformation

Br
Br

(1S,2S,4R)-1,2-Dibromo-4-tert-butylcyclohexane

the presence of the bulky tert-butyl group controls the

orientation of the two bromine atoms added to the ring
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Reaction Stereochemistry

Finally, consider the reaction of an achiral

starting material in an chiral environment
BINAP can be resolved into its R and S enantiomers

PPh2
PPh2
BINAP
(S)-(-)-BINAP
[

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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

using (R)-BINAP-Ru as a hydrogenation catalyst, (S)naproxen is formed in greater than 98% ee

CH3

CH2

COOH
H3 CO

+ H2

(R)-BINAP-Ru
pressure

COOH
H3 CO

(S)-Naproxen
(ee > 98%)

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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)-BINAP-Ru
OH

H2

(E)-3,7-Dimethyl-2,6-octadien-1-ol
(Geraniol)

OH
(R)-3,7-Dimethyl-6-octen-1-ol

(R)-BINAP-Ru

OH
(S)-3,7-Dimethyl-6-octen-1-ol

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Reactions
of Alkenes
End Chapter 6

6-77