Chapter 8

Alkenes and Alkynes II:

Addition Reactions

Ch. 8 - 1
1. Addition Reactions of Alkenes

E
C C + E Nu C C
Nu

Ch. 8 - 2
1A. How To Understand Additions
to Alkenes
 This is an addition reaction: E–Nu
added across the double bond
E
C C + E Nu C C
Nu
π-bond σ-bond 2 σ-bonds

Bonds broken Bonds formed

Ch. 8 - 3
 Since p bonds are formed from the
overlapping of π orbitals, π electron
clouds are above and below the plane
of the double bond

π electron
C C clouds

Ch. 8 - 4
 Electrophilic
● electron seeking
● C=C and C≡C π bonds are
particularly susceptible to
electrophilic reagents (electrophiles)

 Common electrophile
● H+, X+ (X = Cl, Br, I), Hg2+, etc.

Ch. 8 - 5
 In an electrophilic addition, the π
electrons seek an electrophile, breaking
the π bond, forming a σ bond and
leaving a positive charge on the vacant
π orbital on the adjacent carbon.
–
Addition of B to form a σ bond
provides an addition product

Ch. 8 - 6
 δ+ −
δ
E Nu E
C C C C + Nu

Nu E
C C

Ch. 8 - 7
2. Electrophilic Addition of
Hydrogen Halides to Alkenes:
Mechanism and Markovnikov’s
Rule
 Mechanism

δ+ δ− A Nu E
E Nu Nu
C C C C C C

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

C C

Ch. 8 - 9
 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 H
Ch. 8 - 10
 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 - 11
 Markovnikov’s Rule
● In the electrophilic addition of an
unsymmetrical electrophile across a
double bond of an alkene, the more
highly substituted and more
stabilized carbocation is formed as
the intermediate in preference to
the less highly substituted and less
stable one

Ch. 8 - 12
 Markovnikov’s Rule
● Thus
δ+ δ− E Nu E
E Nu

E
NOT

o o o
Note: carbocation stability ⇒ 3 > 2 > 1
Ch. 8 - 13
 Addition of Hydrogen Halides
● Addition of HCl, HBr and HI across
a C=C bond
+
● H is the electrophile

+ − Br
δ δ slow Br
+ H Br
r.d.s fast

Br
NO

Ch. 8 - 14
Ch. 8 - 15
2A. Theoretical Explanation of
Markovnikov’s Rule
δ+ δ− H H
H3C 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)
 One way to state Markovnikov’s rule is to
say that in the addition of HX to an alkene,
the hydrogen atom adds to the carbon atom
of the double bond that already has the
greater number of hydrogen atoms
Ch. 8 - 16
 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 - 17
Ch. 8 - 18
 Examples
Cl H
H Cl
(1) +
H Cl

(95 : 5)

H Br
H Br
(2) +

Br H
(98 : 2)
Ch. 8 - 19
2B. Modern Statement of
Markovnikov’s Rule
 In the ionic addition of an
unsymmetrical reagent to a double
bond, the positive portion of the added
reagent attaches itself to a carbon
atom of the double bond so as to yield
the more stable carbocation as an
intermediate

Ch. 8 - 20
  Examples OH
OH

Cl Cl

δ+ δ− more stable (major)

Cl OH 3o cation
(1)

Cl Cl
OH

OH

less stable (minor)

1o cation
Ch. 8 - 21
  Examples
Cl
I I
Cl
+ − more stable (major)
δ δ
I Cl 3o cation
(2)

Cl
Cl
I I
less stable (minor)
1o cation Ch. 8 - 22
2C. Regioselective Reactions
 When a reaction that can potentially yield
two or more constitutional isomers actually
produces only one (or a predominance of
one), the reaction is said to be
regioselective
Cl H
H Cl
+
H Cl
(major) (minor)

regioisomers
Regioselectivity: 95 : 5 Ch. 8 - 23
2D. An Exception to Markovnikov’s Rule

Br
H Br (anti-Markovnikov's
RO OR product)
heat H

 Via a radical mechanism (see Chapter 10)

 This anti-Markovnikov addition does not

take place with HI, HCl, and HF, even when
peroxides are present

Ch. 8 - 24
3. Stereochemistry of the Ionic
Addition to an Alkene
X
X
attack from top C CH3
H
Bu

racemate
(S)-2-Halohexane
H H
H X H (50%)
C C C CH2 H
Bu
Bu H
achiral
trigonal planar H
carbocation Bu C CH3
X X
attack from bottom (R)-2-Halohexane
(50%)
Ch. 8 - 25
4. Addition of Sulfuric Acid to Alkenes
OSO3H
conc. H2SO4
cold
H
O
δ− δ+
HO S O H OSO3H
O
H
more stable
o
3 cation H
less stable
 Addition of H–OSO3H o
1 cation
across a C=C bond
Ch. 8 - 26
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 - 27
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 H3O+
(e.g. dilute H2SO4, H3PO4)
Ch. 8 - 28
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 - 29
5B. Rearrangements
 Rearrangement can occur with certain
carbocations
H2O
H
H2SO4

NOT 1,2-alkyl shift

OH
OH
H2O

(major product)
Ch. 8 - 30
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 HCh. 8 - 31
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 - 32
6B. Rearrangements Seldom Occur in
Oxymercuration–Demercuration

 Recall: acid-catalyzed hydration of

some alkenes leads to rearrangement
products
e.g.
OH
H2O
H
H2SO4

Ch. 8 - 33
 H2O
H
H2SO4

1,2-alkyl shift

H H
O
H2O
H H

H2O
OH
H
Ch. 8 - 34
 Rearrangements of the carbon skeleton
seldom occur in oxymercuration–
demercuration
no rearrangement
OH
1. Hg(OAc)2, THF-H2O
2. NaBH4
H

OH
via

Hg(OAc)
Ch. 8 - 35
6C. Mechanism of Oxymercuration
 Does not undergo a “free carbocation”
δ−
OAc
δ+Hg +
δ
HgOAc
OAc
AcO + δ+
H2O

HgOAc HgOAc

H2O
HO O H
H
Ch. 8 - 36
  Stereochemistry
● Usually anti-addition
H2O

Hg(OAc)2 δ+
THF-H2O H3C
H3C H +Hg(OAc)
δ

OH H

CH3 Hg(OAc)
Ch. 8 - 37
 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 Ch. 8 - 38
 Solvomercuration-Demercuration
OR
Hg(O2CCF3)2

THF-ROH
Hg(O2CCF3)

NaBH4
OH−

OR

H
Ch. 8 - 39
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 - 40
 BH3 exists as dimer B2H6 or complex
with coordinative solvent
H H
H B B H
H H

H H Me
H B O H B S
H H Me

(BH3-THF) (BH3-DMS)

Ch. 8 - 41
 syn addition
H OH
1. BH3-THF
−
2. H2O2, OH
H3C H CH3 H

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

Ch. 8 - 42
 Compare with oxymercuration-
demercuration
OH H
Hg(OAc)2
THF-H2O
H3C H CH3 Hg(OAc)

NaBH4
anti addition
OH H

Markovnikov addition
of “H” & “OH” CH3 H
Ch. 8 - 43
8. Hydroboration: Synthesis of
Alkylboranes

hydroboration
C C +H B C C
H B

alkene boron alkylborane

hydride

Ch. 8 - 44
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
π complex

H3C H H3C + H
H H H δ H
H δ−
H B H B
four-atom H
syn addition
H concerted T.S. H
of H and B
Ch. 8 - 45
 Other examples
H BH2-THF
(1) +
H BH2 H2B H
(99 : 1)

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

Ch. 8 - 46
8B. Stereochemistry of Hydroboration

 Syn addition
H BH2

BH3-THF
H3C H CH3 H

Ch. 8 - 47
9. Oxidation and Hydrolysis of
Alkylboranes
δ+
δ−
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 - 48
 Oxidation

O
H2O2
B B
O O

Ch. 8 - 49
 ● 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 - 50
 Hydrolysis

O
B
O O
NaOH
H2O

3 OH + Na3BO3

Ch. 8 - 51
 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 - 52
 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 - 53
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 - 54
 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
2. H2O2, OH− addition of H2O
Ch. 8 - 55
11. Protonolysis of Alkylboranes

CH3CO2H
R B R H + CH3CO2 B
heat
alkylborane alkane

 Protonolysis of an alkylborane takes place

with retention of configuration; hydrogen
replaces boron where it stands in the
alkylborane
 Overall stereochemistry of hydroboration–
protonolysis: syn Ch. 8 - 56
 e.g.

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

via
H3C H
H BH2

Ch. 8 - 57
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
CCl4
Br
(vicinal
dibromide)

Ch. 8 - 58
 Examples
Br Br
Br2
(1) +
o
−5 C
Br Br

(anti addition of Br2) (racemate)

Cl
Cl2 2
(2) Ph Ph
Ph Ph
−10oC 1

(anti addition of Cl2) Cl Ph Ph

same as
Cl Cl
(rotation of C1-C2 bond)
Ch. 8 - 59
12A. Mechanism of Halogen Addition

C C + Br Br C C
Br–Br bond becomes
polarized when close δ+ Br
to alkene
− Br
δ

Br
+ Br
Br Br
(vincinal
Dibromide) (bromonium) Ch. 8 - 60
 Stereochemistry
● Anti addition

Br Br
Br
H H CCl4
Br

H Br SN2 reaction
enantiomer +
Br H
(anti)
Ch. 8 - 61
13. Stereospecific Reactions

 A reaction is stereospecific when a

particular stereoisomeric form of the
starting material reacts by a
mechanism that gives a specific
stereoisomeric form of the product

Ch. 8 - 62
● Reaction 1
H CH3 Br2 Br CH3 Br Br

H C C H H H
CCl4
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
CCl4 Br
H3C CH3 H3C Br CH3
cis-2-Butene (2R,3R) (2S,3S)
(a pair of enantiomers)
Ch. 8 - 63
 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
δ
Br
bromonium H Br
δ−Br
ion H3C C C
(achiral) (b) H
Br CH3
(2S,3S)-2,3-Dibromobutane
(chiral)
Ch. 8 - 64
 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
δ
Br
− bromonium H Br
δ Br
ion H3C C C
(achiral) (b) CH3
Br H
(R,S)-2,3-Dibromobutane
(meso)
Ch. 8 - 65
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 - 66
 Mechanism

H2O
Br Br δ+
H2O H3C
H3C H
+Br
δ

OH H

CH3 Br
H3C H
Br

Ch. 8 - 67
 Other variation
● If H2O is replaced by ROH, RÖH will
be the nucleophile
e.g.
OMe
Br2

MeOH
Br

Ch. 8 - 68
15. Divalent Carbon Compounds:
Carbenes
15A. Structure and Reactions of
Methylene

heat
CH2 N N CH2 + N N
or light
Diazomethane Methylene Nitrogen
(a carbene)

Ch. 8 - 69
CH2 N N H2C N N CH2 N N

I II III

C C + CH2 C C
C
H H
Alkene Methylene Cyclopropane

Ch. 8 - 70
15B. Reactions of Other Carbenes:
Dihalocarbenes
 :CX2 (e.g. :CCl2)
 Generation by α-elimination of
chloroform

H t
O Bu
Cl C CCl2 + tBuOH + Cl
Cl
Cl

Ch. 8 - 71
 Usually a syn (cis) addition across a
C=C bond

t H
BuOK
Cl
CHCl3
Cl
H
(a cyclopropane)

Ch. 8 - 72
 Stereospecific reactions
Cl
Cl
CCl2

Cl
Cl
CCl2

Ch. 8 - 73
15C. Carbenoids: The Simmons-Smith
Cyclopropane Synthesis

I ZnI
CH2I2 + Zn(Cu) C
H2
(Zinc-copper (a carbenoid)
couple)

Ch. 8 - 74
 A stereospecific syn (cis) addition
across a C=C bond
CH2I2

Zn(Cu)
(trans) (trans)

CH2I2

Zn(Cu)

(cis) (cis)
Ch. 8 - 75
16. Oxidation of Alkenes:
Syn 1,2-Dihydroxylation
 Overall: addition of 2 OH groups across
a C=C bond

C C
OH OH

⊖
 Reagents: dilute KMnO4 / OH / H2O /
cold or OsO4, pyridine then NaHSO3,
H2O
Ch. 8 - 76
16A. Mechanism for Syn
Dihydroxylation of Alkenes
dil. KMnO4
C C
OH−, H2O OH
O O C C
cold H2O
Mn OH OH
O O
+ MnO2
C C

C C
NaHSO3
O O C C
OsO4 H2O
pyridine Os OH OH
O O
+ Os
Ch. 8 - 77
 Both reagents give syn dihydroxylation

dil. KMnO4
H H
OH−, H2O, cold
or OsO4, pyridine
then NaHSO3
H H
OH OH
(cis-diol)

Ch. 8 - 78
 Comparison of the two reagents
● KMnO4: usually lower yield and
possibly side products due to over-
oxidation
OH
1. KMnO4, ∆
+ O
+ O
2. H
OH
(oxidative cleavage of C=C)
● OsO4: usually much higher yield but
OsO4 is extremely toxic
Ch. 8 - 79
17. Oxidative Cleavage of Alkenes
17A. Cleavage with Hot Basic
Potassium Permanganate
O
a −
KMnO4, OH , H2O
b b 2 a O
a ∆ b
or H3O+
a a
O
b b
2 a OH
b
Ch. 8 - 80
 Other examples
1. KMnO4, OH−, H2O, heat
(1) + O
2. H3O
+
O C O

1. KMnO4, OH−, H2O, heat O

(2)
2. H3O+ O

OH
Ch. 8 - 81
17B. Cleavage with Ozone

R R" 1. O3 R R"
O + O
2. Zn, AcOH
R' H R' H
or Me2S

Ch. 8 - 82
 Examples
O
1. O3
(1)
2. Zn, AcOH

1. O3 O
(2)
2. Me2S
H
+

Ch. 8 - 83
 Mechanism
C C C C C + C
O O O O
O O
O O initial ozonide
O

O
C O
C C C Zn(OAc)2 +
O O O O

ozonide C O + O C

Ch. 8 - 84
18. Electrophilic Addition of
Bromine & Chlorine to Alkynes
X X
X2 (excess)
R C C H R C C H
CH2Cl2
(X = Cl, Br, I) X X

X H X X
X2 X2
R C C H C C R C C H
H X X X
(anti-addition)
Ch. 8 - 85
 19. Addition of Hydrogen Halides
to Alkynes
X H
H X (excess)
R C C H R C C H
(X = Cl, Br, I)
X H
 Regioselectivity
● Follow Markovnikov’s rule
Br H Br H
HBr HBr
H3C C C H C C CH3 C C H
CH3 H Br H
gem-dibromide
Ch. 8 - 86
 Mechanism

H
H Br Br
CH3 C C H CH3 C C
H
Br H
C C
CH3 H

Br H H
Br Br H Br
CH3 C C H C C H
CH3
Br H H
Ch. 8 - 87
 Anti-Markovnikov addition of hydrogen
bromide to alkynes occurs when
peroxides are present in the reaction
mixture

H Br
Br
peroxides
H

(E) and (Z)

(74%)

Ch. 8 - 88
20. Oxidative Cleavage of Alkynes
1. O3
R C C R' RCO2H + R'CO2H
2. HOAc
OR
1. KMnO4, OH−
R C C R' RCO2H + R'CO2H
2. H3O+

 Example
1. O3
Ph C C CH3 PhCO2H + CH3CO2H
2. AcOH
Ch. 8 - 89
21. How to Plan a Synthesis:
Some Approaches & Examples
 In planning a synthesis we often have
to consider four interrelated aspects:
1. Construction of the carbon
skeleton
2. Functional group interconversions
3. Control of regiochemistry
4. Control of stereochemistry

Ch. 8 - 90
21A. Retrosynthetic Analysis

 How to synthesize ?
OH

● Retrosynthetic analysis

OH
(target molecule) (precursor)
Ch. 8 - 91
 Markovnikov addition
● Synthesis of H2O
H+
H2O
OH

or 1. Hg(OAc)2, THF-H2O
2. NaBH4, OH−

Ch. 8 - 92
 How to synthesize OH
?

● Retrosynthetic analysis

OH
(target molecule) (precursor)

● Synthesis
1. BH3-THF
2. H2O2, OH− OH

anti-Markovnikov addition of H2O

Ch. 8 - 93
21B. Disconnections, Synthons, and
Synthetic Equivalents
 One approach to retrosynthetic
analysis is to consider a retrosynthetic
step as a “disconnection” of one of the
bonds

 In general, we call the fragments of a

hypothetical retrosynthetic
disconnection Synthons
Ch. 8 - 94
 Example
How? Br Br
Ph H CH3
Ph

● Retrosynthetic analysis
Br Br
(i) CH3 Ph CH3
Ph

(gem-dibromide came from addition

of HBr across a C≡C bond)
Ch. 8 - 95
 ● Retrosynthetic analysis
synthons

(ii) Ph CH3 Ph + CH3

disconnection

H3C I + Ph Na

synthetic equivalent
Ch. 8 - 96
 ● Synthesis

NaNH2
Ph H Ph Na
liq. NH3
-30oC H3C I
(via an SN2
reaction)

Br Br HBr
CH3 Ph CH3
Ph (excess)

Ch. 8 - 97
21C. Stereochemical Considerations

How? Br Br
H3C CH3
H3C CH3

Ch. 8 - 98
 Retrosynthetic analysis
● The precursor of a vicinal dibromide
is usually an alkene
● Bromination of alkenes are anti
addition Br
Br Br
CH3
H3C
H3C CH3
Br
o
(rotate 180 ) (anti addition
of Br2)
(anti addition of H2)
CH3
H3C CH3 H3C
Ch. 8 - 99
 ● Synthesis

1. Li, liq. NH3

H3C CH3 CH3
H3C
2. NH4Cl
(anti addition of H2)
(anti
Br2/CCl4
addition
Br of Br2)
Br Br same
CH3
as H3C
H3C CH3
Br
Ch. 8 - 100
 END OF CHAPTER 8 

Ch. 8 - 101