Chapter 7: Alkenes: Reactions and Synthesis

H OH H H
C C C C

alcohol alkane

X OH HO OH
C C C C

halohydrin C C 1,2-diol

alkene
X X C O
C C
carbonyl
1,2-dihalide

H X C
C C C C

halide halide

Addition

X Y
C C + X Y C C

alkene

Elimination

Electrophilic Addition
H
H Br
ether
+ HBr
H H
H

Dehydrohalogenation: loss of HX from an alkyl halide to form

an alkene
H EtOH H
Br (ethanol)
+ KOH + KBr + H2O

H H
H

1
 Hydration: addition of water (H-OH) across a double bond to
give an alcohol
H
H OH
H+
+ H2O
H H
H

Dehydration: Loss of water (H-OH) from an alcohol to give an

alkene

H H
OH H+
+ H2O

H H
H

Addition of Halogens (X2) to Alkenes: 1,2-dihalides

X2 X X
C C C C

alkene 1,2-dihalide

Br Br
+ Br2 +
Br Br

not observed

1,2-dibromide has the anti stereochemistry

Bromonium ion intermediate controls the stereochemistry

2
Halohydrin Formation
"X-OH" X OH
C C C C

alkene halohydrin

Br2, H2O X
+ HBr
OH

anti
stereochemistry

Organic molecules are sparingly soluble in water as solvent. The reaction is often
done in a mix of organic solvent and water using N-bromosuccinimide (NBS) as
the electrophilic bromine source.
O OH O

Br
DMSO, H2O N H
+ N Br +

O O

Note that the aryl ring does not react!!!

For unsymmterical alkenes, halohydrin formation is

Markovnikov-like in that the orientation of the addition of
X-OH can be predicted by considering carbocation stability
d+ CH3
more d+ charge on the
Br d+ more substituted carbon
d+

H2O adds in the second step and adds to the

carbon that has the most d+ charge and ends
up on the more substituted end of the double bond

HO
CH3 Br2, H2O CH3

Br
H
Br adds to the double bond first (formation of
bromonium ion) and is on the least substituted
end of the double bond

3
Hydration of Alkenes: addition of water (H-OH) across the p-bond
of an alkene to give an alcohol.

1. Acid catalyzed hydration- Markovnikov addition of H-OH

Not a good method for hydration of an alkene

2. Oxymercuration- Markovnikov addition H-OH

CH3 1) Hg(OAc)2, H2O HO
CH3
2) NaBH4

H
H

3. Hydroboration- Anti-Markovnikov addition of H-OH,

Syn addition of H-OH
1) B2H6, THF H
CH3 CH3
2) H2O2, NaOH, H2O

H
HO

H _
H H
B B O
2 H3B O
H H +
H tetrahydrofuran
(THF)
B2H6 (diborane) borane-THF
complex

4
Reaction of Alkenes with Carbenes to give Cyclopropanes

Carbene: highly reactive, 6-electron species.

(sp2-hybridized)

Generation and Reaction of Carbenes:

CHCl3 + KOH Cl2C: + H2O + KCl

dichlorocarbene

H
CHCl3, KOH
Cl
Cl
H

Simmons-Smith Reaction (cyclopropanation)

ether
CH2I2 + Zn(Cu) I-CH2-Zn-I = “H2C:”
methylene
carbene
H
CH2I2, Zn(Cu)

ether
H

5
The cyclopropanation reaction of an alkene with a carbene takes place
in a single step. There is NO intermediate.

As such, the geometry of the alkene is preserved in the product.

Groups that are trans on the alkene will end up trans on the
cyclopropane product. Groups that are cis on the alkene will end
up cis on the cyclopropane product.

H H CH2I2, Zn(Cu)
H H
R R ether R R

cis-alkene cis-cyclopropane

H R CH2I2, Zn(Cu)
H R
R H ether R H

trans-alkene trans-cyclopropane

Hydrogenation: Addition of H2 across the p-bond of an alkene to

give an alkane. This is a reduction.
H2, PtO2

ethanol

• The reaction uses H2 and a precious metal catalyst.

• The catalysts is not soluble in the reaction media, thus this process
is referred to as a heterogenous catalysis.
• The catalyst assists in breaking the p-bond of the alkene and
the H-H s-bond.
• The reaction takes places on the surface of the catalyst. Thus, the rate
of the reaction is proportional to the surface area of the catalyst.
• To increase the surface area of the catalyst it is finely dispersed on
an inert support such as charcoal (carbon, C)
• Carbon-carbon p-bond of alkenes and alkynes can be reduced to the
corresponding saturated C-C bond. Other p-bond bond such as
C=O (carbonyl) and C≡N are not easily reduced by catalytic
hydrogenation. The C=C bonds of aryl rings are not easily reduced.

6
Catalysts: Pt2O (Adam’s catalyst) or Pd/C
mechanism:

The addition of H2 across the p-bond is syn

O O
H2, PtO2

ethanol

O
H2, Pd/C
C5H11 OH CH3(CH2)16CO2H
Linoleic Acid (unsaturated fatty acid) Steric Acid (saturated fatty acid)
O
O
OCH3 H2, Pd/C
OCH3
ethanol

H2, Pd/C C
C
N N
ethanol

H CH3
CH3 H2, PtO2 CH3 H

ethanol CH3
CH3 CH3
H H

syn addition
of H2 Not observed

7
Oxidation of Alkenes to 1,2-Diols and Carbonyl

Hydroxylation: formal addition of HO-OH across the p-bond of an

alkene to give a 1,2-diol. This is an overall oxidation.

1) OsO4 H
2) NaHSO3 OH
syn addition
OH
H

H
O O osmate ester intermediate
Os
O O - not usually isolate
H
- NaHSO3 breaks down the
osmate ester to the product

Ozonolysis: oxidative cleavage of an alkene to carbonyl compounds.

The p- and s-bonds of the alkene are broken and replaced with
C=O doubled bonds.

C=C of aryl rings, C≡N and C=O do not react with ozone,
C≡C react very slowly with ozone

electrical +
Ozone (O3): 3 O2 discharge
2 O3 O _
O O

O3, CH2Cl2 O
R1 R3 -78 °C O O O O Zn R1 R3
R1 R3 O + O
R2 R4 R1 R3 R2 R4
O R2 R4
R2 R4
molozonide ozonide + ZnO

8
 1) O3
2) Zn
O + O

1) O3
2) Zn
H +
O=
O C
H2

1) O3
2) Zn O

H
O

Oxidative Cleavage of 1,2-Diols to Carbonyl Compounds

HO OH NaIO4 R1 R3
O + O
R1 R3
THF, H2O R2 R4
R2 R4
+ ZnO
OH
O O
I
O O
R1 R3 periodate intermediate
R2 R4

OH NaIO4 O
H
H
OH
O