Alkenes

Addition Reactions
Synthesis
 Addition of HBr or HCl
Markovnikov Addition
CH3 H Br H
HBr CH3 H
C C C C
CH3 H CH3 H
Markovnikov

H Br
CH3 H
C C
CH3 H
not formed
HBr Addition with RO-OR
Anti-Markovnikov

HBr H Br

RO-OR, h
 Free-Radical Mechanism

Initiation: .
RO-OR 2 RO
. . + ROH
RO + HBr Br

. Br
Propagation: i) + Br .

Br H Br
ii) . .
+ 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

Br Br
Br2
+
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
Br Br
Br2 in H2O

bromonium ion
H2O
Br
Br

OH
OH
H
Br
Unsymmetrical Bromonium ion
H2O opens ring at more hindered site

+

Br Br
+ CH3

CH3 HO H
H
H2O
Br and OH are trans in
anti addition

Br
Br2 in H2O
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
OH H
CH3 H H2SO4 (aq) CH3 H
C C C C
CH3 catalytic CH3
H H
H
-H

H 2O H 2O H
H OH H
CH3 H CH3 H
C C C C
CH3 H CH3 H
Oxymercuration Hydration
Markovnikov addition
Regiospecific Reaction

1) Hg(OAc)2 in
THF/H2O OH

2) NaBH4
H
 Oxymercuration Mechanism

HgOAc OAc
+
 OAc OAc
Hg Hg
Hg(OAc) 2
+
in H2O  OH
OH2
OAc H OAc
Hg
NaBH4 (H )

OH OH H
organomercurial alcohol
Predict the Oxymercuration
Hydration Products
What Alkene would you use to
Make These Alcohols?
 Hydroboration Hydration
Anti-Markovnikov
Syn addition

1) BH3-THF H OH
3 3
2) H2O2, NaOH
BH3 adds to Alkene
 Hydroboration
H H
BH3 H BH2 H B 2
3

Alkylborane

H
H 2O 2 H OH
B - 3
H H OH

Trialkylborane
Regiochemistry is
Anti-Markovnikov
Syn Addition of H2O
Draw the Major Products

1) BH3, THF
2) H2O2, NaOH
CH3

1) Hg(OAc)2, H2O-THF

2) NaBH4
2 Complementary Hydration
Reactions
1) BH3, THF OH

2) H2O2, NaOH H
CH3
CH3

1) Hg(OAc)2, H2O-THF
OH
2) NaBH4
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 H H
 In situ Preparation of Carbene

H C
H H H

sp2 hybridized

Zn
I I I I
C + Zn C C + ZnI2
H H H H H H
carbene
Two MCAD Inhibitors

CO2H CO2H

MCPA SPA
 Epoxide Preparation
From Alkenes
O O O
RCOOH
H H + RCOH
in CH2Cl2
R O
C Cl CO3H
O H
O MCPBA

meta chloroperoxybenzoic acid

Epoxide Preparation
From Halohydrins
Br
Br2 in H2O
OH + enantiomer
CH3 CH3

NaH

O + H2 + NaCl

CH3
 Mechanism

O H O O
H:

Br Br
bromohydrin intramolecular S N2
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 O
 Ozonolysis Forms
2 Carbonyl Compounds
 Ozonolysis
Alkene Cleavage

CH3 CH3 1) O3 in CH 2Cl2 CH3 CH3

C=C C O +O C
2) CH3SCH3 + DMSO
H CH3 H CH3
or Zn/HOAc
DMS
O
O O O
O O O O
CH3 CH3
C=C H O
H
H CH3
ozonide
Mechanism of Ozonolysis
What Alkene will Undergo Ozonolysis
to Give the Products Shown?
 Addition polymers

n
n
isoprene
polyisoprene (a trimer)
latex, rubber (tires)
Air Pollution Reacts with Tires

n
rubber

O3

O O O
?
O O O
O O O
O3 reacts with all alkene  Bonds
CH2
O O O O
1) O3
+ HCH
2) CH3SCH3 H H

CH2
O
O

O O
 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 O
O

H2 butanone

B H
H