Alkene reactions

1. Hydrohalogenation (Addition of HX)

a. Polar mechanism
Alkyl halide
Alkene
H-X X
Regiochemistry: Markovnikov addition
Stereochemistry: not stereospecific
(X = Cl, Br, or I)
Rearrangments: possible

b. Radical mechanism
Alkyl bromide
Alkene Regiochemistry: Anti-Markovnikov addition
Br
H-Br Stereochemistry: not stereospecific
Rearrangments: none
RO-OR
2. Hydration (Addition of H2O)
a. Acid-catalyzed hydration
Alcohol
Alkene
H-O-H OH
Regiochemistry: Markovnikov addition
Stereochemistry: not stereospecific
H2SO4 or H3PO4
Rearrangments: possible

b1. Oxymercuration-demercuration
Alcohol
Alkene
1. Hg(OAc)2, H2O OH
Regiochemistry: Markovnikov addition
2. NaBH4 Stereochemistry: not stereospecific
Rearrangments: none

b2. Alkoxymercuration-demercuration
Ether
Alkene
1. Hg(OAc)2, ROH OR
Regiochemistry: Markovnikov addition
2. NaBH4 Stereochemistry: not stereospecific
Rearrangments: none
c. hydroboration-oxidation
Alkene Alcohol
Regiochemistry: Anti-Markovnikov addition
1. BH3 . THF
Stereochemistry: syn-addition
2. H2O2, NaOH(aq) Rearrangments: none
OH

3. Catalytic hydrogenation (Addition of H2)

Alkene Alkane

H2 Regiochemistry: N/A
Stereochemistry: syn-addition
Pt or Pd or Ni or Rh Rearrangments: none
4. Halogenation (Addition of X2)
Alkene vicinal dihalide

X2 X Regiochemistry: N/A
Stereochemistry: anti-addition
solvent: non-nucleophilic X
Rearrangments: none
X = Cl or Br

5. Halohydrin formation (X2/H2O)

Alkene halohydrin
Regiochemistry: OH adds to more substituted C
OH
X2 Stereochemistry: anti-addition
H 2O Rearrangments: none
X
X = Cl or Br

6. Syn-dihydroxylation
Alkene vicinal diol

1.OsO4 OH

2. H2O2 or NaHSO3/H2O OH Regiochemistry: N/A

OR Stereochemistry: syn-addition
KMnO4 OH Rearrangments: none

cold, dilute, slightly basic OH

7. Oxidative cleavage
H OH
O O
H O HO O
H H OH OH
O O
H O HO O

O O
H O HO O

O O
O O

a. Ozonolysis
H
1. O3 O
H O
2. (CH3)2S
or H
Zn, H3O+

b. Permanganate oxidation (KMnO4)

OH
KMnO4 O
HO O
hot, concentrated
OH
Alkyne reactions

1. Formation of acetylide ions

terminal alkyne very strong base alkynide (acetylide) ion

NaNH2
H3C H H 3C
or
NaH

2. Reactions with acetylide ions

a. Alkylation of acetylide ions

terminal alkyne 1. NaNH2 alkyne mech: SN2

limitations: R = methyl of
H 3C H 2. R-X H3C R unhindered 1o
competing mech: E2

1. NaNH2
ex:
H 3C H
2. CH3CH2-X
b. Addition of acetylide ions to carbonyl compounds
terminal alkyne 1. NaNH2
H
H 3C H O H 3C OH
2. (could be an aldehyde
or a ketone) H
H H
3. H3O+

1. NaNH2
ex: H3CH2C H
O
2.
H3C H
3. H3O+
3. Synthesis of alkynes by elimination reactions
vicinal dihalide alkyne
geminal dihalide alkyne

X very strong base

X very strong base

heat heat
X
X
+ 2 HX + 2 HX

a. using molten KOH

internal alkyne
X X KOH (fused or molten)
200oC

b. using NaNH2
terminal alkyne
X X 1. NaNH2 / 150oC

2. H2O
4. Hydrohalogenation (addition of HX)
a. polar mechanism
vinyl halide geminal dihalide
alkyne
H-X X H-X X X
Regiochemistry: Markovnikov addition
(X = Cl, Br, or I)

b. radical mechanism
vinyl halide geminal dihalide
alkyne
H-Br H-Br
Br Regiochemistry: Anti-Markovnikov
Br
ROOR
Br

5. Halogenation (addition of X2)

tetrahalide
Alkyne X X X
X2 X2

CCl4 CCl4 X X
X
X = Cl or Br
6. Hydrogenation (addition of H2)
a. Reduction to alkanes (catalytic hydrogenation)
cis-alkene alkane
alkyne
H2 H2

Pt or Pd or Ni or Rh Pt or Pd or Ni or Rh

b. Reduction to cis-alkenes (use of poisoned catalyst)

alkyne cis-alkene
H2
Regiochemistry: N/A
Lindlar's catalyst Stereochemistry: syn-addition
(Pd/BaSO4, CH3OH Rearrangments: none
quinoline)

or

Ni2B

c. Reduction to trans-alkenes (dissolving metal reduction)

trans-alkene Regiochemistry: N/A
alkyne Na or Li
Stereochemistry: anti-addition
NH3 (l) Rearrangments: none
7. Hydration (addition of H2O)
a. Oxymercuration-demercuration
alkyne enol ketone
HgSO4, H2O OH enol-keto tautomerization O
Regiochemistry: Markovnikov
H2SO4

b. Hydroboration-oxidation
enol aldehyde
alkyne
1. BH3 . THF enol-keto tautomerization O
OH
2. H2O2, NaOH (aq) H

or

1. 9-BBN Regiochemistry: Anti-Markovnikov

2. H2O2, NaOH (aq)

or

1. Sia2BH . THF

2. H2O2, NaOH (aq)

8. Oxidative cleavage
alkyne
OH O
+
O HO OH

O
O
+ HO
OH

a. Ozonolysis
alkyne
1. O3 OH O
+
O HO OH
2. H2O

O
1. O3 O
+ HO
2. H2O OH

b. Permanganate oxidation
alkyne
KMnO4 OH O
+
O HO OH
hot, conc.

O
KMnO4 O
+ HO
hot, conc. OH