Alkenes

Addition Reactions
Synthesis

Addition of HBr or HCl

Markovnikov Addition
H

CH3
C
CH3

C
H

HBr

CH3

Br H
C

CH3
H
Markovnikov
CH3
CH3

Br

H
not formed

HBr Addition with RO-OR

Anti-Markovnikov

HBr
RO-OR, h

H Br

Free-Radical Mechanism
Initiation:

RO-OR

2 RO

. + ROH

RO + HBr

ii)

Br

Propagation: i)

+ Br

Br

Br

H Br
+ H-Br

+ Br

Addition of Br2
Br2

Br
Br

A Similar Mechanism to the

Addition of HBr?

Trans is formed exclusively

(No cis is formed)

Carbocation can be Stabilized

by Neighboring Br

Bromonium Ion is Opened

Equally from Both Sides
Br2
+

Br

Br

Br

Br

Br

Br

Br

Br

Br

Br

Definitions
Stereospecific only one stereoisomer is
formed at the expense of the other (e.g.
trans vs. cis)
Stereoselective one stereoisomer is
formed preferentially over the other.

Anti-Addition
Stereospecific Reaction
Anti-addition
Br2

Br

Br
+
Br

Br

Bromonium Ion Intermediate

+

Br

Br

Br
Br

Br

Br
Br
Bromonium ion

Halohydrins

Bromohydrin Formation
Addition of Br OH
Stereospecific & Regiospecific
+
Br

Br

Br2 in H2O

Br

Br

bromonium ion
Br

Br

OH
H

Br
OH

H2O

Unsymmetrical Bromonium ion

H2O opens ring at more hindered site

CH3
H2O

Br
H

CH3
HO

Br
H

Br and OH are trans in

anti addition
Br2 in H2O

Br
OH

CH3

CH3

Catalytic Hydrogenation
syn addition

Mechanism Syn Addition

Syn Addition of H2

H2, 1% Pt/C
75 psi
CH3

CH3

CH3 H H CH3
cis only

Hydrogenation

all alkene bonds are reduced

Three mol equivalents of hydrogen gas are consumed

H2, Pt/C

Hydrogenated Vegetable Oil

Hydration
Addition of H2O
CH3
CH3

H
C

CH3

H2SO4 (aq)
catalytic

C
H

CH3

OH H
C

C
H

H
-H
H2O

H2O
CH3
CH3

H
C

C
H

H
CH3
CH3

OH H
C

C
H

Oxymercuration Hydration
Markovnikov addition
Regiospecific Reaction
1) Hg(OAc)2 in
THF/H2O
2) NaBH4

OH
H

Oxymercuration Mechanism
HgOAc OAc
+

Hg(OAc)2
in H2O
Hg

OAc
Hg

Hg

OH
H

OH2

OAc
NaBH4 (H )

OH
organomercurial alcohol

OH H

OAc

OAc

Predict the Oxymercuration

Hydration Products

What Alkene would you use to

Make These Alcohols?

Hydroboration Hydration
Anti-Markovnikov
Syn addition

1) BH3-THF
2) H2O2, NaOH

H OH
3

BH3 adds to Alkene

Hydroboration
H BH2

BH3

H H
H B

Alkylborane

H
H

H2O2
H

Trialkylborane

OH

H OH
3

Regiochemistry is
Anti-Markovnikov

Syn Addition of H2O

Draw the Major Products

1) BH3, THF
CH3

2) H2O2, NaOH

1) Hg(OAc)2, H2O-THF
2) NaBH4

2 Complementary Hydration
Reactions
1) BH3, THF
CH3

2) H2O2, NaOH

1) Hg(OAc)2, H2O-THF
2) NaBH4

OH
H
CH3
OH
CH3

Oxymercuration the more highly

substituted alcohol forms
Hydroboration the less highly
substituted alcohol forms

Predict Both Oxymercuration

and Hydroboration Products

Cyclopropanation

A Carbene is Similar to
Geometry of a Carbocation

Dichlorocarbene Reactions

Simmons-Smith Reaction
CH2I2, Zn(Cu)
in ether

In situ Preparation of Carbene

H
H

sp2 hybridized
Zn
I

I
C

I
+ Zn

I
C

C
H

+ ZnI2

H
carbene

Two MCAD Inhibitors

CO2H
MCPA

CO 2H
SPA

Epoxide Preparation
From Alkenes
O

RCOOH
in CH2Cl2
R

C
O

O
O

Cl
H

O
H

CO3H
MCPBA

meta chloroperoxybenzoic acid

+ RCOH

Epoxide Preparation
From Halohydrins
Br

Br2 in H2O

OH
CH3

+ enantiomer

CH3
NaH

O
CH3

+ H2 + NaCl

Mechanism
O H
Br
bromohydrin

H:
Br

intramolecular SN2

Epoxide groups are Common in

Biologically Active Molecules
Periplenone B
female cockroach sex pheromone
O

O
O

A New Class of Anti-tumor Agents

Epothilone B
anticancer drug from soil bacteria
O
S
H

OH

N
O
O

OH

Ozonolysis Forms
2 Carbonyl Compounds

Ozonolysis
Alkene Cleavage
CH3

CH3
C=C

CH3

CH3

CH3

1) O3 in CH2Cl2

2) CH3SCH3
or Zn/HOAc

O +O

C
CH3

H
DMS

O
CH3
H

C=C

O
CH3
CH3

O
H

O O
H

O
ozonide

+ DMSO

Mechanism of Ozonolysis

What Alkene will Undergo Ozonolysis

to Give the Products Shown?

Addition polymers

n
isoprene

polyisoprene (a trimer)
latex, rubber (tires)

Air Pollution Reacts with Tires

rubber
O3

O
O

O
O

O
O

O3 reacts with all alkene Bonds

CH2
O

1) O3
2) CH3SCH3

CH2
O
O

O
H

+ HCH

Problem
A symmetrical unknown compound A,
C8H16, reacts with H2 on a 1% Pt/C catalyst
to form B (C8H18). Treatment of A with O3
followed by Zn/HOAc affords butanone
only. Identify A and B.
O
CH3CCH2CH3
butanone

O3
A

H2

H
H

O
O
butanone