ADDITION REACTIONS

2. Electrophilic Addition of
Hydrogen Halides to Alkenes:
Mechanism and Markovnikov’s
Rule
 Mechanism

  A Nu E
E Nu Nu
C C C C C C

Ch. 8 - 2
 Mechanism
● Sometimes do not go through a “free carbocation”, may go via

C C

Ch. 8 - 3
 Markovnikov’s Rule
● For symmetrical substrates, no problem for regiochemistry

H H E E
E Nu same
C C H C C H as H C C H
H H H H H H

Nu

E Nu Nu E
same
H C C H as H C C H
H H H HCh. 8 - 4
 Markovnikov’s Rule
● But for unsymmetrical substrates, two regioisomers are possible

H3C H E E
E Nu
C C CH3 C C H or CH3 C C H
H H H H H H

Nu Nu

E Nu different Nu E
CH3 C C H from CH3 C C H
H H H H
Ch. 8 - 5
 Markovnikov’s Rule
● Thus

  E Nu E
E Nu

E
NOT

Note: carbocation stability  3o > 2o > 1o

Ch. 8 - 6
 Addition of Hydrogen Halides
● Addition of HCl, HBr and HI across a C=C bond
● H+ is the electrophile

  Br
  slow Br
+ H Br
r.d.s fast

Br
NO

Ch. 8 - 7
Ch. 8 - 8
 2A. Theoretical Explanation of
Markovnikov’s Rule

 
H3C H H H
H X
C C CH3 C C H or CH3 C C H
step 1
H H H H H H
(slow
r.d.s.) 2o carbocation 1o carbocation
(more stable) (more stable)

Ch. 8 - 9
 H H

☓
Br

(1o cation) fast Br

(minor)
H Br
slow
(r.d.s.)
H H
Br

(2o cation) fast

Br
(major)

Step 1 Step 2
Ch. 8 - 10
 Examples

Cl H
H Cl
(1) +
H Cl

(95 : 5)

H Br
H Br
(2) +

Br H
(98 : 2)
Ch. 8 - 11
Also check Solomons Global edition page# 340, section 8.2
3. Stereochemistry of the Ionic
Addition to an Alkene
X
X
attack from top C CH3
H
Bu
(S)-2-Halohexane

racemate
H H
H X H (50%)
C C C CH2 H
Bu
Bu H
achiral
trigonal planar H
Bu
carbocation C CH3
X X
attack from bottom (R)-2-Halohexane
(50%) Ch. 8 - 12
4. Addition of Sulfuric Acid to Alkenes

OSO3H
conc. H2SO4
cold
H
O
 
HO S O H OSO3H
O H
more stable
o
3 cation H
 Addition of H–OSO3H across a C=C bond less stable
1o cation
Ch. 8 - 13
 4A. Alcohols from Alkyl Hydrogen
Sulfates

OSO3H OH
conc. H2SO4 H2O
cold heat
H H

 The overall result of the addition of sulfuric acid to an alkene followed by hydrolysis is
the Markovnikov addition of H – and –OH

Ch. 8 - 14
5. Addition of Water to Alkenes:
Acid-Catalyzed Hydration
 Overall process
● Addition of H–OH across a C=C bond
● H+ is the electrophile
● Follow Markovnikov’s rule

OH H
H2O
dilute H 3O+
(e.g. dilute H2SO4, H3PO4) Ch. 8 - 15
5A. Mechanism

H
H O H H2O

H H
slow fast

(step 1) (step 2)
O
more stable H H
3o cation
fast H2O
(step 3)

H H
H O H +
OH Ch. 8 - 16
 5B. Rearrangements
 Rearrangement can occur with certain
carbocations
H2O
H
H2SO4

NOT 1,2-alkyl shift

OH
OH
H2O

(major product) Ch. 8 - 17

6. Alcohols from Alkenes through
Oxymercuration–Demercuration:
Markovnikov Addition

 Step 1: Oxymercuration

Hg(OAc) 2
C C C C
THF-H2O
HO HgOAc

 Step 2: Demercuration

NaBH4
C C C C
OH
HO HgOAc HO H Ch. 8 - 18
 6A. Regioselectivity of Oxymercura-
tion–Demercuration

 Oxymercuration–demercuration is also highly regioselective and follows

Markovnikov’s rule

Hg(OAc) 2 HgOAc
NaBH4

THF-H2O OH
HO
H

HO Ch. 8 - 19
 6C. Mechanism of Oxymercuration
 Does not undergo a “free carbocation”


OAc
Hg 
HgOAc
OAc
AcO + 
H2O

HgOAc HgOAc

H2O
HO O H
H Ch. 8 - 20
  Stereochemistry
● Usually anti-addition

H2O

Hg(OAc) 2 
THF-H2O H3C
H3C H Hg(OAc)


OH H

CH3 Hg(OAc) Ch. 8 - 21

 Although attack by water on the bridged mercurinium ion leads to anti addition of the
hydroxyl and mercury groups, the reaction that replaces mercury with hydrogen is not
stereocontrolled (it likely involves radicals). This step scrambles the overall
stereochemistry
 The net result of oxymercuration–demercuration is a mixture of syn and anti addition
of –H and –OH to the alkene

OH H OH H OH D
NaBD4
+
CH3 H
CH3 Hg(OAc) CH3 D

Ch. 8 - 22
 Solvomercuration-Demercuration

OR
Hg(O 2CCF 3)2

THF-ROH
Hg(O 2CCF 3)

NaBH4
OH

OR

H
Ch. 8 - 23
7. Alcohols from Alkenes through
Hydroboration–Oxidation:
Anti-Markovnikov Syn Hydration

"BH3"
C C C C
H BH2

 Addition of H–BH2 across a C=C bond

Ch. 8 - 24
 syn addition

H OH
1. BH3-THF
2. H2O2, OH
H3C H CH3 H

Anti-Markovnikov addition
of “H” & “OH”

Ch. 8 - 25
 Compare with oxymercuration-demercuration

OH H
Hg(OAc) 2
THF-H2O
H3C H CH3 Hg(OAc)

anti addition NaBH4

OH H
Markovnikov addition
of “H” & “OH”

CH3 H Ch. 8 - 26
8. Hydroboration: Synthesis of
Alkylboranes

hydroboration
C C +H B C C
H B
alkene boron alkylborane
hydride

Ch. 8 - 27
 8A. Mechanism of Hydroboration
H3C H H3C H H3C H

H H H H H H
+ H
H H B
H H B H
H B H
H
 complex

H3C H H3C  H
H H H  H
H 
H B H B
four-atom H
syn addition
H concerted T.S. H
of H and B Ch. 8 - 28
 Other examples

H BH2-THF
(1) +
H BH2 H2B H
(99 : 1)

H BH2-THF
(2) +
H BH2 H2B H
(98 : 2)

Ch. 8 - 29
 8B. Stereochemistry of Hydroboration

 Syn addition

H BH2

BH3-THF
H3C H CH3 H

Ch. 8 - 30
9. Oxidation and Hydrolysis of
Alkylboranes


H B H H BH2
H
H B

B always ends B B
up on the least H
H
hindered carbon
(trialkyl borane) Ch. 8 - 31
 Oxidation

O
H2O2/NaOH
B B
O O

Ch. 8 - 32
 ● Via

R R
R3B O OH R B O OH B
R OR
R

R R
HO O O OH
B R B OR
RO OR
O
OH
R OR
O B OR B
RO OR
HO OR
Ch. 8 - 33
 Hydrolysis

O
B
O O
NaOH
H2O

3 OH + Na3BO3

Ch. 8 - 34
 Overall synthetic process of hydroboration-oxidation-hydrolysis

1. BH3-THF
2. H2O2
3. NaOH, H2O H OH

● Overall: anti-Markovnikov addition of H–OH across a C=C bond

● Opposite regioisomers as oxymercuration-demercuration

Ch. 8 - 35
 anti-Markovnikov
 Example syn addition

H BH2
BH3-THF

H3C H CH3 H

H OH H2O2
OH

CH3 H
This oxidation step occurs with retention of configuration

Ch. 8 - 36
10. Summary of Alkene Hydration
Methods
Summary of Methods for Converting Alkene to Alcohol

Occurrence of
Reaction Regiochemistry Stereochemistry Rearrangements
Acid-catalyzed Markovnikov Not controlled Frequent
hydration addition

Oxymercuration- Markovnikov Not controlled Seldom

demercuration addition

Hydroboration- Anti-Markovnikov Stereospecific: Seldom

oxidation addition syn addition of
H – and –OH
Ch. 8 - 37
 Examples
via H
1,2-hydride
H shift

H OH with
H
rearrangement
H2O
OH
1. Hg(OAc)2, THF-H2O H
2. NaBH4, OH
Markovnikov addition of H2O
without rearrangement

H anti-Markovni-
1. BH3-THF OH kov, syn addition
2. H2O2, OH of H2O
Ch. 8 - 38
 e.g.

1. BH3-THF
H3C H
2. CH3CO2D
H3C H H D
+ enantiomer

via
H3C H
H BH2

Ch. 8 - 39
12. Electrophilic Addition of Bromine
and Chlorine to Alkenes

 Addition of X–X (X = Cl, Br) across a C=C bond

Br
Br2
C C C C
CCl 4
Br
(vicinal
dibromide)

Ch. 8 - 40
 Examples

Br Br
Br2
(1) +
o
5 C
Br Br

(anti addition of Br2) (racemate)

Cl
Cl2 2
(2) Ph Ph
Ph 10oC 1 Ph

(anti addition of Cl2) Cl Ph Ph

same as
Cl Cl
(rotation of C1-C2 bond)
Ch. 8 - 41
 12A. Mechanism of Halogen Addition

C C + Br Br C C
Br–Br bond becomes
polarized when close  Br
to alkene
 Br

Br
+ Br
Br Br
(vincinal
Dibromide) (bromonium) Ch. 8 - 42
 Stereochemistry
● Anti addition

Br Br
Br
H H CCl 4
Br

H Br SN2 reaction
enantiomer +
Br H
(anti) Ch. 8 - 43
● Reaction 1

H CH3 Br2 Br CH3 Br Br

H C C H H H
CCl 4
H3C H H3C Br H3C CH3
trans-2-Butene (2R,3S)-2,3-Dibromobutane
(a meso compound)
● Reaction 2

H H Br H H Br
Br2
C C CH3 + H3C C C
H H
CCl 4 Br
H3C CH3 H3C Br CH3
cis-2-Butene (2R,3R) (2S,3S)
(a pair of enantiomers)
Ch. 8 - 44
 Addition of bromine to cis-2-Butene

Br H
(a) CH3
H C C
H3C Br
(a) Br (b) (2R,3R)-2,3-Dibromobutane
(chiral)
H H
H H H3C CH3
C C C C
H3C CH3
 Br

Br
bromonium H Br
Br
ion H3C C C
(achiral) (b) H
Br CH3
(2S,3S)-2,3-Dibromobutane
(chiral)
Ch. 8 - 45
 Addition of bromine to trans-2-Butene

Br CH3
(a)
H C C H
H3C Br
(a) Br (b) (R,S)-2,3-Dibromobutane
(meso)
H CH3
H CH3 H3C
C C C C H
H3C H
 Br

Br
bromonium H Br
Br
ion H3C C C
(achiral) (b) CH3
Br H
(R,S)-2,3-Dibromobutane
(meso)
Ch. 8 - 46
14. Halohydrin Formation

X2 OH
C C C C
H2O
X

 Addition of –OH and –X (X = Cl, Br) across a C=C bond

+
 X is the electrophile
 Follow Markovnikov’s rule

Ch. 8 - 47
 Mechanism

H2O
Br Br 
H2O H3C
H3C H
Br


OH H

CH3 Br
H3C H
Br

Ch. 8 - 48
 Other variation
● If H2O is replaced by ROH, RÖH will be the nucleophile

e.g.
OMe
Br2

MeOH
Br

Ch. 8 - 49
9. Radical Addition to Alkenes: The
Anti-Markovnikov Addition of

Hydrogen Bromide

 Anti-Markovnikov addition of HBr to alkenes – peroxide effect

● Addition of HBr to alkenes usually follows Markovnikov’s rule

Br H not H Br
HBr

Ch. 10 - 50
● In the presence of peroxides (RO–OR), anti-Markovnikov addition is observed

H Br not Br H
HBr

RO OR
heat

Ch. 10 - 51
 Mechanism
● Via a radical mechanism

heat
RO OR 2 RO
(homolytic cleavage)
(chain initiation)

RO + H Br ROH + Br

Ch. 10 - 52
 Br +
Br
o
(3 radical, more stable)

Br
not Br +

o
(1 radical, less stable)
H
+ H Br + Br
Br Br Ch. 10 - 53
 Hydrogen bromide is the only hydrogen halide that gives anti-Markovnikov addition
when peroxides are present

 Hydrogen fluoride, hydrogen chloride, and hydrogen iodide do not give anti-
Markovnikov addition even when peroxides are present Br
HBr

(via more stable

2o carbocation)

HBr Br
RO-OR
heat (via more stable
2o radical)Ch. 10 - 54