Chapter 6

Reactions of Alkenes

6-1

Table of Contents

An overview of the reactions of alkenes

Reactive intermediates involved in organic
g
reactions
Electrophilic addition reactions of alkenes with
bromines or mercuric acetate
Hydroboration reactions of alkenes with borane
O id ti
Oxidation
reactions
ti
off alkenes
lk
with
ith osmium
i
tetroxide
Reduction reactions of alkenes with hydrogen and
palladium
Stereochemistry
y derived from the reactions of
alkenes
6-2

Reactions of Alkenes

The most characteristic reaction of alkenes is

addition to the carbon-carbon double bond.
The pi bond is broken.
In its place, sigma bonds form to two new atoms or
groups off atoms.
t

6-3

Characteristic Reactions
Descriptive Name(s )

Reaction

C C

HCl
( H X)

C C

+ H2 O

C C

C C

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

Br2
( X2 )
Br2
( X2 )

H2 O

HO
C C
Br( X)

Hydrochlorination
(hydrohalogenation)
Hydration

Bromination
(halogenation)
Halohydrin formation
(Bromohydrin
formation)
6-4

Characteristic Reactions
C C

+ Hg(OAc) 2

C C

BH3

C C

OsO4

C C

H2

H2 O

HgOAc
Oxymercuration
C C
HO
C C
H BH2

Hydrob
y
oration

C C
HO OH

D iol formation
(oxidation)

C C
H H

Hydrogenation
(reduction )

The first five reactions are classified as anti-addition

reactions and the remaining three are syn-addition
reactions.
6-5

Reaction Mechanisms

A reaction mechanism describes how a reaction

occurs.
Which bonds are broken and which new ones are
formed.
The
Th order
d and
d relative
l ti rates
t off th
the various
i
b
bondd
breaking 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.

6-6

Gibbs Free Energy

Gibbs free energy change, G0

A thermodynamic function relating enthalpy, entropy,
and
d ttemperature.
t

G 0 = H 0 TS0
Exergonic reaction:
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
products.
Endergonic reaction:
reaction: A reaction in which the Gibbs free
energy of the products is higher than that of the
reactants;
t t the
th position
iti off equilibrium
ilib i
ffor an endergonic
d
i
reaction favors starting materials.

6-7

Gibbs Free Energy

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

H 0 < 0

S0 > 0

G 0 > 0; th e
position of equilib riu m
favors reactants

At h igh er temperatures
w hen TS0 > H0 an d
G 0 < 0, th e position of
equ ilibrium favors
products
p

At low er temp eratu res

w hen TS0 < H0 an d
G 0 < 0, th e position of
equ ilibrium favors
products

G 0 < 0; th e
position of equilib riu m
favors products

6-8

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,
reaction : The difference in enthalpy
between reactants and products.
Exothermic reaction:
reaction: A reaction in which the enthalpy of
th products
the
d t is
i llower th
than th
thatt off the
th reactants;
t t a
reaction in which heat is released.
Endothermic reaction:
reaction: A reaction in which the enthalpy
py
of the products is higher than that of the reactants; a
reaction in which heat is absorbed.

6-9

Energy Diagrams

Energy diagram:
diagram: A graph showing the changes in
energy
gy that occur during
g a chemical reaction.
Reaction coordinate:
coordinate: A measure in the change in
positions of atoms during a reactions progression.

6-10

Activation Energy

Transition state:
state:
An unstable species of maximum energy formed during
th course off a reaction.
the
ti
A maximum on an energy diagram.

Activation Energy,
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
small, many collisions occur with sufficient
energy to reach the transition state; reaction is fast.

6-11

Energy Diagram
An energy diagram for a one-step reaction with no
intermediate.

6-12

Energy Diagram

Figure 6.1 An energy diagram for a two-step

reaction with one intermediate.

6-13

Developing a Reaction Mechanism

How a mechanism is developed

Design experiments to reveal the details of a particular chemical
reaction.
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 not mean that the mechanism is correct, only that it is the
best explanation we are able to devise
devise.
Mechanisms are the framework within which to organize descriptive
chemistry.
Mechanisms
M h i
provide
id an iintellectual
ll
l satisfaction
i f i d
derived
i d ffrom
constructing models that accurately reflect the behavior of chemical
systems.
Mechanisms
M h i
are ttools
l with
ith which
hi h tto search
h ffor new iinformation
f
ti and
d
new understanding.
6-14

Electron pushing

Organic chemists use a technique called electron

pushing,
g alternativelyy called arrow pushing,
g to
depict the flow of electrons during a chemical
reaction. In so doing, the following rules must be
b
d
obeyed.
Rule 1: Arrows are used to indicate movement of
electrons.
electrons

6-15

Electron Pushing

Rule 2: Arrows are never used to indicate the

movement of atoms.

6-16

Electron Sources and Sinks

Rule 3 Arrows always start at an electron source

and end at an electron sink.
Electron source: Most commonly a bond or a lone
pair of electrons on an atom.
Electron
El t
sink:
i k: An
A atom
t
in
i a molecule
l
l or iion th
thatt can
accept a new bond or a lone pair of electrons.

Rule 4 Bond breaking will occur to avoid overfilling

valence (hypervalence) on an atom serving as an
electron sink

6-17

Patterns of Electron Movement

In the reaction mechanisms we will describe in this

and following
g chapters, curved arrows can be
classified by these patterns.
1. Redistribution of bonds and/or lone pairs.
2. Formation of a new bond from a lone pair or a
bond.
3. Breaking a bond to give a new lone pair or a
bond.

6-18

Characteristic Mechanism Elements

Pattern 1: Make a new bond between a

nucleophile (source
for an arrow)) and an
(
electrophile (sink for an arrow).

6-19

Characteristic Mechanism Elements

Pattern 2: Break a bond so that relatively

stable molecules or ions are created.

6-20

Characteristic Mechanism Elements

Pattern 3: Add a proton Use this pattern when

there is a strong
g acid present or a molecule that
has a strongly basic functional group.

6-21

Characteristic Mechanism Elements

Pattern 4: Take a proton away. Use this pattern

when a molecule has a strongly
g y acidic proton or
there is a strong base present.

6-22

Electrophilic Additions
Electrophilic Addition: A common type of reaction with
alkenes in which an electrophilic species adds to a
b d
bond.
Hydrohalogenation using HCl, HBr, HI
Hydration using H2O in the presence of H2SO4
Halogenation using Cl2, Br2
Halohydrination
y
using
g HOCl,, HOBr
Oxymercuration using Hg(OAc)2, H2O followed by
reduction
A characteristic pattern of the mechanism of each
reaction is making a bond between a nucleophile
( bond)) and an electrophile
p
(the
(
reagent).
g )
6-23

Addition of HX

Carried out with pure reagents or in a polar solvent such as

acetic acid.
Br H

CH3 CH= CH 2 + H Br
Propene

Br

CH3 CH- CH 2 + CH3 CH- CH 2

2-Bromopropane 1-Bromopropane
((not observed))

Addition is regioselective
Regioselective reaction:
reaction: An addition or substitution
reaction in which one product is formed in preference to
all others that might be formed.
Markovnikov
Markovnikovs
s rule:
rule: In the addition of HX or H2O to an
alkene, H adds to the carbon of the double bond having
the greater number of hydrogens.

6-24

HBr + 2-Butene

A two-step mechanism
Step 1: Make a new bond between a nucleophile ( bond) and an
electrophileadd a proton.

Step 2: Make a new bond between a nucleophile and an

electrophile.

6-25

Carbocations

Carbocation: A species in which a carbon atom has only

Carbocation:
six electrons in its valence shell and bears a positive
charge.
charge
Carbocations:
Are classified as 1, 2, or 3 depending on the number
of carbons bonded to the carbon bearing the + charge.
Are electrophiles; that is, they are electron-loving.
acids.
Are Lewis acids
Have bond angles of approximately 120 about the
positively charged carbon.
Use
U sp2 hybrid
h b id orbitals
bit l tto fform sigma
i
b
bonds
d ffrom carbon
b
to the three attached groups.
y
2p
p orbital lies p
perpendicular
p
to the
The unhybridized
sigma bond framework and contains no electrons.
6-26

Carbocations

Figure 6.3 The structure of the tert-butyl cation.

6-27

Carbocation Stability
relative stability
H

H
C+

H
Methyl
cation
(meth yl)

CH3

H
C+
H

Ethyl
cation
(1)

CH3

CH3
C+

H
Isopropyl
cation
(2)

CH3

CH3
C+

CH3
t ert-Bu tyl
cation
(3)

Increasin g carbocation s tability

Methyl and primary carbocations are so unstable that

theyy are never observed in solution.

6-28

Carbocation Stability
We can account for the relative stability of carbocations
if we assume that alkyl groups bonded to a positively
charged
h
d carbon
b are electron
l t
releasing
l
i and
d th
thereby
b
delocalize the positive charge of the cation.
electron releasing ability of alkyl
We account for this electron-releasing
groups by (1) the inductive effect, and (2)
hyperconjugation.

6-29

The Inductive Effect

The positively charged carbon polarizes electrons of
adjacent sigma bonds toward it.
The positive charge on the cation is thus delocalized
over nearby atoms.
The larger the volume over which the positive charge is
delocalized, the greater the stability of the cation.

6-30

Hyperconjugation
Involves partial overlap
of the -bonding orbital
off an adjacent
dj
tC
C-H
H or C
CC bond with the vacant
2p orbital of the cationic
carbon.
The result is
delocalization of the
positive charge.

6-31

HBr + 2-Butene

Figure 6.4 An energy diagram for the two-step

addition of HBr to 2-butene.
The reaction is exergonic.

6-32

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 (to the carbon bearing the
greater number of hydrogens).
HOH adds in accordance with Markovnikovs rule.
CH3 CH=CH2 + H2 O
Propene
CH3
CH3 C=CH2 + H2 O
2-Methylprop
y p p ene

H2 SO4

OH H
CH3 CH-CH2
2-Propanol

CH3
CH3 C-CH2
HO H
2-Methyl-2-propanol
y
p p

H2 SO4

6-33

Acid-Catalyzed Hydration of Propene

Step 1: Make a new bond between a nucleophile (
bond) and an electrophile add a proton.
CH 3 CH= CH 2 + H O H

slow, rate
slow
determining

CH 3 CHCH 3

:O H

A 2 carbocation
intermediate

CH 3 CHCH 3 +

Step 2: Make a new bond between a nucleophile

((H2O)) and an electrophile
p
((a carbocation intermediate))
to give an oxonium
ion
ion.
+
: O-H

fast

O+

Step 3: Take a proton away.

fast

CH3 CHCH 3 + H O H
: OH
H
:

O:

O+

H
H
An oxonium ion
:

CH3 CHCH 3

CH3 CHCH 3

6-34

Carbocation Rearrangements

In electrophilic addition to alkenes, there is the

possibilityy for rearrangement
g
if a carbocation is
involved.
Rearrangement:: A change in connectivity of the
Rearrangement
atoms in a product compared with the connectivity
of the same atoms in the starting material.

6-35

Carbocation Rearrangements
In addition of HCl to an alkene.
Cl
+ HCl
3,3-D imethylbu te
tenee
1-bu

Cl

2-Ch loro-3,3-dimethylbutan e 2-Chloro-2,3-dimethylbu tane

(thee eexp
(t
p ected p rodu
odu ct; 17%)
7%)
(thee major
(t
ajo p rodu
odu ct; 83%)

In acid-catalyzed
acid catalyzed hydration of an alkene
alkene.
+ H2 O
3
3-Methyl-1-buten
1
e

H2 SO4

OH
2 M th l 2 b t oll
2-Methyl-2-butan

6-36

Carbocation Rearrangements
The driving force is rearrangement of a less stable
carbocation to a more stable one.
CH 3

CH 3 C- CHCH 3 + : Cl :
:

Cl :

CH 3

CH 3 CCH= CH 2 + H
H
3-Methyl-1-butene

slow, rate
determining

H
A 2 carbocation
intermediate

The less stable 2

2 carbocation rearranges to a more
stable 3 carbocation by 1,2-shift of a hydride ion.
CH 3
CH 3 CC CHCH 3
+

fast

CH 3
CH 3 CC CHCH 3
+

H
A 3 carbocation

6-37

Carbocation Rearrangements
Reaction of the more stable carbocation (an
electrophile) with chloride ion (a nucleophile) completes
th reaction.
the
ti
If possible, a carbocation will always rearrange to a
more stable one.
CH3

CH3 C- CH2 CH3 + : Cl :

+

fast

CH3

CH3 C- CH2 CH3

: Cl :

2 Chl
2-Chloro-2-methylbutane
2
th lb t

6-38

Addition of Cl2 and Br2

Carried out with either the pure reagents or in an inert
solvent such as CH2Cl2.
Br Br
CH3 CH=CHCH3
2-Buten e

Br2

CH2 Cl2

CH3 CH-CHCH3
2,3-D ib romob utane

Addition of bromine or chlorine to a cycloalkene gives a

trans-dihalocycloalkane as a racemic mixture.
Br
+

Cyclohexene

Br2

CH2 Cl 2

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
6-39

Addition of Cl2 and Br2

Step 1: Make a new bond between a nucleophile
( bond) and an electrophile. The product is a bridged
b
i
iion iintermediate.
t
di t
bromonium

6-40

Addition of Cl2 and Br2

Step 2: Make a new bond between a nucleophile and
an electrophile from the side opposite the bromonium
iion, which
hi h opens th
b d ring.
i
the th
three-membered

6-41

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, the trans enantiomers
are formed as a racemic mixture.
B
Br

B2
Br

Br

Br

Br
(1S,2S)-1,2-D ibromocyclohexan
l h
e

Br

Br

B
Br
Br
(1R,2R)-1,2-D ibromocyclohexane

6-42

Addition of HOCl and HOBr

Treatment of an alkene with Br2 or Cl2 in water

forms a halohydrin.
y
Halohydrin:: A compound containing -OH and -X
Halohydrin
on adjacent carbons.
CH3 CH= CH 2 + Cl 2 + H2 O
Propene

HO
O Cl
C
CH3 CH- CH2

+ HCl

1-Chloro-2-propanol
(a chlorohydrin)

6-43

Addition of HOCl and HOBr

Reaction is both regioselective (OH adds to the more
substituted carbon) and anti stereoselective.
Both selectivities are illustrated by the addition of HOBr
to 1-methylcyclopentene.
Br2 / H 2 O

OH
Br

1-Methylcyclopentene

OH

+ HBr

Br

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

To account for the regioselectivity and the anti

stereoselectivity, chemists propose a three-step
mechanism (next two screens)
screens).
6-44

Addition of HOCl and HOBr

Step 1: Make a new bond between a nucleophile (
bond) and an electrophile to give a bromonium ion
iintermediate.
t
di t

6-45

Addition of HOCl and HOBr

Step 2: Make a new bond between a nucleophile (H2O)
and an electrophile (the bromonium ion intermediate)

H O:

H
R

H
R

:Br :
C

H
H

:Br :

Step 3 Take a proton away.

H
R
C

Br
C

H
R

Br

H
H

+ H3 O+

C
H

O H
H

6-46

Addition of HOCl and HOBr

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.

6-47

Addition of HOCl and HOBr

Bridged bromonium ion from propene.

6-48

Oxymercuration/Reduction

Oxymercuration followed by reduction results in

hydration
y
of a carbon-carbon double bond.
oxymercuration
OH
Hg(OAc)
(OA ) 2 + H2 O
+ H
1-Pen tene

Mercu ry(II)
acetate

O
+ CH3 COH

HgOAc
An organ omercury
comp ou
o nd

A cetic
acid

reduction
OH

OH
NaBH4
HgOAc

H
2-Pen tanol

O
+ CH COH + Hg
3
Acetic acid
6-49

Oxymercuration/Reduction
An important feature of oxymercuration/reduction is that
it occurs without rearrangement, unlike acid-catalyzed
additions
dditi
off water
t to
t alkenes.
lk
1 . Hg(OAc) 2 , H2 O
2 . NaBH
N BH4

OH
3,3-D imeth yl-2-b utanol

3,3-D imeth yl-1-b utene

Oxymercuration occurs with anti stereoselectivity.

Cyclopentene

Hg
g ( OAc ) 2
H2 O

N aBH4

OH

Hg OA c

(Anti addition of
OH and HgOAc)

OH

H
H
Cyclopentanol

6-50

Oxymercuration/Reduction. Mechanism
Step 1: Break a bond to give stable molecules or
ions.
+
AcO- Hg
AcO
Hg- OAc

AcO Hg + AcO
AcO(an electrophile)

Step 2: Make a new bond between a nucleophile (

bond) and an electrophile
electrophile.

6-51

Oxymercuration/Reduction
Step 3: Make a new bond between a nucleophile
(H2O) and an electrophile at the more substituted
b tto open th
b d ring.
i
carbon
the th
three-membered

Step 4: Reduction of the C-HgOAc bond.

6-52

Oxymercuration/Reduction

Anti stereoselective
Formation of a bridged
g mercurinium ion intermediate
and anti attack of the nucleophile to open the threemembered ring.

R i
Regioselective
l ti
The more substituted carbon of the mercurinium ion
intermediate has the greater degree of partial positive
character.
Computer modeling indicates that the C-Hg bond to the
more substituted carbon of the bridged intermediate is
longer than the one to the less substituted carbon.
ring-opening
opening transition state is reached more easily
The ring
by attack at the more substituted carbon.
6-53

Hydroboration/Oxidation

Hydroboration: The addition of borane, BH3, to an

Hydroboration:
alkene to form a trialkylborane.
y
H
H B

CH2 CH3
+ 3 CH2 = CH2

H
Borane

CH2 CH3
Triethylborane
(a trialkylborane)

Borane dimerizes to diborane, B2H6.

2 BH3
Borane

CH3 CH2 B

B2 H6
D iborane

Although borane exists as diborane

diborane, in terms of
reactivity it behaves as BH3.
6-54

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

Tetrahydrofuran
((THF))

+ :O BH3
BH3 TH F

6-55

Hydroboration/Oxidation

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

CH3

1-Methylcyclopentene

BH3

H3 C

BR2
H
(Syn addition of BH 3 )
(R = 2-methylcyclopentyl)

6-56

Hydroboration/Oxidation. Mechanism
Concerted regioselective and syn stereoselective
addition of B and H to the carbon-carbon double bond.
A
Approach
h iis thi
this way b
because B iis llarger th
than H
H.

H B
H
CH3 CH2 CH2 CH= CH2

CH3 CH2 CH2 CH-CH 2

Trialkylboranes are rarely isolated.

Oxidation with alkaline hydrogen peroxide gives an
alcohol and sodium borate.
R3 B + H2 O2 + NaOH
A trialkylt i lk l
borane

3 ROH + Na3 BO3

A alcohol
An
l h l
6-57

Hydroboration/Oxidation. Mechanism

Hydrogen peroxide oxidation of a trialkylborane

Step
and
p 1: Make a new bond between a nucleophile
p
an electrophile. The hydroperoxide anion forms by the
reaction of HOOH with hydroxide ion.

6-58

Hydroboration/Oxidation. Mechanism
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

O-H

Step 3: Reaction of the trialkylborane with aqueous

NaOH gives the alcohol and sodium borate.
( RO) 3 B + 3NaOH
A trialkylborate

3ROH + Na3 BO3

Sodium borate

6-59

Oxidation/Reduction

Oxidation:: The loss of electrons.

Oxidation
Alternatively,
y the loss of H, the g
gain of O, or both.

Reduction:: The gain of electrons.

Reduction
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.
solution.
solution
3. Complete a charge balance using electrons, e-

6-60

Oxidation/Reduction
Balanced half-reactions for the hydration, oxidation and
reduction of propene.
OH

CH 3 CH= CH2 + H2 O
Propene

CH3 CHCH3
2-Propanol
HO OH

CH 3 CH= CH2 + 2 H2 O
Propene
CH3 CH= CH2 + 2 H+ + 2 e Propene

CH 3 CHCH 2 + 2 H + + 2 e 1,2-Propanediol
CH3 CH2 CH3
Propane

6-61

Oxidation with OsO4

OsO4 oxidizes an alkene to a glycol

glycol, a compound with OH
groups on adjacent carbons. Note that OsO4 is both
expensive and highly toxic
toxic.
Oxidation is syn stereoselective.
OsO 4

O O
Os
O O
A cyclic osmate

OH
N aHSO 3
H2 O

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

O
OsO
O4 is
i used
d iin catalytic
t l ti amounts
t with
ith another
th oxidizing
idi i
agent to reoxidize its reduced forms of osmium and,
thus, recycle OsO4. Two commonly used oxidizing
agents
t are
CH3
HOOH
Hyd rogen
peroxid e

CH3 COOH
CH3
t ert -Bu tyl h yd roperoxide
(t -BuOOH)

NaHSO3 : sodium hydrogen sulfite (or sodium bisulfite)

6-62

Oxidation with OsO4.

O

Os

Os
O

O
O

2 H 2O

OH

Os
OH

HO

OH

6-63

Oxidation with O3

Treatment of an alkene with ozone followed by a

weak reducing
g agent
g
cleaves the C=C and forms
two carbonyl groups in its place. In the following
example, the weak reducing agent is
di th l lfid (CH3)2S.
dimethylsulfide,
S
CH3
CH3 C= CHCH 2 CH 3
2-Methyl-2-pentene

O
1 . O3
CH3 CCH3
2 . ( CH3 ) 2 S
Propanone
(a ketone)

O
+ HCCH 2 CH3
Propanal
(an aldehyde)

6-64

Oxidation of alkene with ozones:

Mechanism:
(1) Formation of molozonide

Syn-addition

:O

CH3

H
H3C

H3C

CH3
H

6-65

Oxidation with O3. Ozonolysis of Alkenes

The initial product is a molozonide which rearranges to
an isomeric ozonide.
CH3 CH= CH CH 3
2-Butene

O3

CH3 CH- CHCH3

A molozonide
H

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

H3 C

Step 2:
O
O

O
C

molozonide
rearrangement

O
C

C
O

O
6-66

Oxidation of alkenes with ozone.

Mechanism
Step 3:

H
H3C

O
C

C
O

CH3

H3C
S

H3C

CH3

CH3

O
H

:O :
+

CH3

H3C

6-67

Reduction of Alkenes

Most alkenes react with H2 in the presence of a

transition metal catalyst
y to give
g
alkanes.
+ H2
Cyclohexene

Pd
25C, 3 atm
Cyclohexane

Commonlyy used transition metal catalysts

y
are Pt, Pd,
Ru, and Ni.
The process is called catalytic reduction or,
alternatively catalytic hydrogenation.
alternatively,
hydrogenation
Addition occurs with syn stereoselectivity.

6-68

Reduction of Alkenes

Figure 6.7 Mechanism of catalytic hydrogenation.

(a) H2 and alkene are absorbed on metal surface.

(b) An H is transferred to the alkene, making a
new C-H bond.
(c) The second C-H bond is formed and the alkane is
released.
6-69

Reduction of Alkenes
Even though addition occurs with syn stereoselectivity,
some product may appear to result from trans addition.
CH 3

CH3

H 2 / Pt

CH 3

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

1,2-Dimethylcyclohexene

CH3
CH3
30% to15%
t 15%
trans -1,2-Dimethylcyclohexane
((racemic))

Reversal of the reaction after the addition of the first

hydrogen gives an isomeric alkene.
CH3
CH3
1,2-D imeth ylcyclohexene

H2 / Pt
H

CH3
H
Pt
H CH3

CH3
CH3
1,6-D imeth ylcyclohexene
6-70

H0 of Hydrogenation

Eth yle ne

S tru ctural
Formu la
CH2 =CH2

Prop en e

CH3 CH=CH2

N ame

H
[[k J ((k cal)/m
) ol]]
-137 (-32.8)
-126 (-30.1)

1-Bu te ne

-127 (-30.3)

cis -2-Bu ten e

-120 (-28.6)

t rans -2-Bu te ne

-115 (-27.6)

2-M eth yl-2-b uten e

-113 (-26.9)

2,3-D ime th yl-2-b ute n e

-111 (-26.6)
6-71

H0 of Hydrogenation

Reduction of an alkene to an alkane is exothermic.

There is net conversion of one p
pi bond to two sigma
g
bonds.

H0 depends on the degree of substitution of the

carbon atoms of the double bond.
The greater the substitution, the lower the value of H

H0 for
f a trans-alkene
t
lk
iis llower th
than th
thatt off an
isomeric cis-alkene.
A trans-alkene
trans alkene is more stable than an isomeric ciscis
alkene.

6-72

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
A
ill see, th
the stereochemistry
t
h i t off th
the product
d t
for some reactions depends on the
stereochemistry of the starting material; that is,
is
some reactions are stereospecific
stereospecific..
6-73

Reaction Stereochemistry

We have seen that bromine adds to 2-butene to

give 2,3-dibromobutane.
g
CH3 CH=CHCH3
2-Buten
2
Buten e

Br2

CH2 Cl2

Br Br
CH3 CH-CHCH3
2,3-D
2,3
D ib romob utane

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
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?
6-74

Bromination of cis-2-Butene
Step 1: Make a bond between a nucleophile ( bond)
and an electrophile.

6-75

Bromination of cis-2-Butene
Step 2: Make a new bond between a nucleophile and
an electrophile.

6-76

Bromination of trans-2-Butene
Step 1: make a new bond between a nucleophile (
bond) and an electrophile.

6-77

Bromination of trans-2-Butene
Step 2: Make a new bond between a nucleophile and
an electrophile.

6-78

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
B
i ti off trans-2-butene
t
2b t
gives
i
meso-2,323
dibromobutane.

Stereospecific reaction:
reaction: A reaction in which the
stereochemistry of the product depends on the
stereochemistryy of the starting
g material.

6-79

Oxidation of 2-Butene
OsO4 oxidation of cis-2-butene gives meso-2,3butanediol.
H
H
H3 C

C
H
H3 C

CH3
cis-2-Butene
( hi l)
(achiral)

OsO4

CH3

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

ROOH

id entical;
a meso
compoun d

OH

HO
2

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

6-80

Oxidation of 2-Butene

OsO4 oxidation of an alkene is stereospecific.

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

H
2

C
H

CH3

H3 C
H
trans-2-Buten e
(achiral)

OsO4

CH3
H

HO
OH
(2S,3S)-2,3-Butaned iol

ROOH
OH

HO
2

a pair of
enantiomers;
a racemic
mixture

CH3
H
H
H3 C
(2R,3R)-2,3-Butaned iol

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

optically
ti ll iinactive).
ti )
6-81

Reaction Stereochemistry

We have seen two examples in which reaction of

achiral starting
g materials g
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)
inactive).

These examples illustrate a very important point

about the creation of chiral molecules
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).
6-82

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-t ert -Bu tylcyclohexene

Br
Br

redraw as
a chair
con formation

Br
Br

(1S,2S,4R)-1,2-D ibromo-4-t ert -b utylcycloh exane

The presence of the bulky tert-butyl group controls the

orientation of the two bromine atoms added to the ring.

6-83

Addition of bromine to 4-tertbutylcyclohexene

y y

H
Br

H
H

Br

Br

Br

Br

Br

6-84

Problem 6.34

Treating 4-penten-1-ol with bromine in water forms

a cyclic
bromoether. Propose a mechanism for the
y
formation of this product.

6-85

Problem 6.34

Step 1: Make a new bond between a

nucleophile (( bond)) and an electrophile. This
reaction of the alkene with bromine gives a
bridged bromonium ion (next screen).

6-86

Problem 6.34

Step 2: Make a new bond between a

nucleophile and an electrophile. Reaction of
the bromonium ion intermediate with the hydroxyl
group followed by proton transfer gives the cyclic
th
ether.

6-87

Problem 6.34

Step 3: Take a proton away. A chiral center has

been created, so a racemic mixture is produced.

6-88

Reactions
of Alkenes
End Chapter 6

6-89