台灣大學開放式課程

有機化學乙
蔡蘊明 教授

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Chapter 8
Alkenes and alkynes: addition reactions

C C + X-Y C C
X Y
electrophilic
electron rich
nucleophilic

Energetics:
break 1π form 2σ
1σ
In general: exothermic
※ Hydrohalogenation:
addition of H-X

C C + H-X C C
H X

例
CH3CH=CHCH3 + HCl
Cl

Br
+ HBr
◎ Regioselectivity

+ HCl Cl
Cl
0%

Cl
+ HCl Cl

0%

Markovnikov’s rule:
H adds to the C having more H
◎ Mechanism
slow Formation of high
C C + H+ C C
+ E intermediate
H

fast
C C + X− C C Bond formation only
+
H H X

H C C+ TS has very high

δ
H + X− carbocation character
δ+
(key for the regioselectivity)

C C
+
H
+ X−

C C + H+ X−

C C
H X
◎ Reason for the regioselectivity
a Formation of a more stable
+ carbocation is faster (lower Ea)
+ H+

b +

+ Cl−
+ Cl

a 3o carbocation is
+ very stable:
Cl
good selectivity
+ H+ and very fast rate

b +
◎ Stereochemistry

+ HCl * racemic mixture

Cl
Mechanism:
+ H+
+

H3C H
+
achiral
CH2
CH3

Cl−
H H
Cl CH3 H3C Cl

Et
1:1 Et
equal probability from both side
※ Addition of H2SO4 (sulfuric acid)

O O
−
+ H O S OH + + O S OH
O H O

concentrated

*Alkenes dissolve in sulfuric H O

O
S
acid but not alkanes OH
O
an alkyl hydrogen sulfate
 Markovnikov
+ H2SO4
OSO3H addition product
Isopropyl hydrogen sulfate

Reason: formation of more stable carbocation

 Alkyl hydrogen sulfate hydrolyzes very easily

O
heat
R O S OH + H2O ROH + H2SO4
O

Very good LVG

※ Acid catalyzed hydration

H+ Addition of water:
+ H2O
hydration
H OH

Mechanism:
slow
+ H3O+ + + H2O
H

+ + H2O
+
H H OH
H

+ H2O + H3O+
+
H OH H OH
H Catalyst is regenerated
In large amt. of H2O (solv.)  equilibrium shifts to the right
例 H3PO4
CH3CH2OH
H2C CH2 + H2O
o
300 C
H+
+ H2O OH
o
25 C

Summary:
 Formation of more stable cabocation  reacts faster
 Follow Markovnikov’s rule
 The reaction is reversible
Recall: acid catalyzed dehydration
H+
−H2O
H OH

Le Chatelier's principle applies:

removes water  dehydrates
！Problems:
rearrangement of carbocation
H2SO4

H2O HO

Mechanism:

+ H+ +
+

H2O −H+

HO
※ Oxymercuration-demercuration:
addition of H2O without rearrangement
O
C C + Hg(OCCH3)2 + H2O C C + AcOH
HO HgOAc

Hg(OAc)2 OH− NaBH4

O
C C + Hgo + CH3CO−

Mechanism: HO H
:OH2 +
H2O + HO
−H
+
Hg HgOAc HgOAc
Hg
AcO OAc OAc
a bridged carbocation

◎ Stereochemistry: anti + syn (lost selectivity at the final step)

◎ Regiochemistry: follow Markovnikov’s rule

例 1) Hg(OAc)2 OH
2) NaBH4, OH−

1) Hg(OAc)2
−
2) NaBH4, OH 94%
OH
no rearrangement
O
1) Hg(OCCF3)2, ROH

2) NaBH4, OH− RO H

A method to synthesize ethers

※ Hydroboration-oxidation
H H H
Diborane B2H6 ≡ H
B
H
B
H
+ −
B2H6 + O BH3
O
tetrahydrofuran borane THF complex
(THF)

◎ Hydroboration: + H B C C
C C
H B
boron
hydide an organoborane

+ BH3
H BH2 H B Pr H B Pr
H Pr

Pr3B
tripropyl borane
◎ Regioselectivity
B on less substituted C

Reasons:
1. Steric
Go through a concerted four center TS
(bond breaking and formation in concert)
R R
H B B H

better steric interaction

2. Electronic
R C C
δ+ δ−
δ− δ+
H B Boron has smaller electronegativity
◎ Stereochemistry
syn-addition
H CH3
+ H B
H CH3 B H

◎ Oxidation

BH3-THF H2O2
3 (CH3CH2CH2)3B 3 CH3CH2CH2OH
−
OH
Mechanism:
CH2CH2CH3 CH2CH2CH3
−
(CH3CH2CH2)2B + OOH (CH3CH2CH2)2B O
OH

(CH3CH2CH2O)3B (CH3CH2CH2)2B OCH2CH2CH3

OH−
OH
B + 3 CH3CH2CH2O− BO33− + 3 CH3CH2CH2OH
HO OH

★ The alkyl group migrates with retention

Overall:
anti-Markovnikov orientation
syn-addition of H2O
trans
◎ Protonolysis of organoboranes

O O
R B + R-H +
CH3COH ∆ CH3CO B

例
1) BH3 H3C H

2) CH3COD
H3C H
O H D

Overall: reduction of alkenes

syn-addition of H2
※ Halogenation

Addition of bromine and chlorine

Bromination:
rt
C C + Br2 C C
in the dark Br Br
dark CCl4
red vic-dibromide *vic: vicinal
colorless

例: chlorination:
−9 oC CH3CHCHCH3
CH3CH=CHCH3 + Cl2
Cl Cl 100%

−9 oC
+ Cl2 Cl
Cl 97%
◎ Mechanism

One possibility:

C C
C C + Br−
+
+ Br
electrophilic Br δ
Br −
δ
( a temporary dipole)
C C
Br Br
Q: Is this mechanism correct?
Check: Can we explain the stereochemistry?
 CH3 CH3
Br2 Br H H Br
+
H Br Br H
CH3 CH3
cis (2R,3R) (2S,3S)

CH3
Br2 H Br
H Br
CH3
trans meso

A stereospecific reaction:
a particular stereoisomeric starting material
gives a specific stereoisomeric product
Carbocation mechanism:

H H H CH3
H3C CH3 H3C H
cis trans

Br2 Br2
(from top) (from bottom)

Br CH3
+ +
H H H
H3C H through H3C
CH3 Br
single
bond
rotation

Should give the same product

The carbocation mechanism can not explain the

stereochemistry
 ★ The real mechanism:
formation of a bromonium bridge ion
Br Br H H Br
top + CH3 H3C
H H +
H
H3C b a CH H3C Br 1:1 Br H
Br−
Br2 3 CH3
H H (a) (b)
H3C CH3
H H
H3C CH3
+
bottom CH3 CH3
Br
Br H H Br
H Br Br H
CH3 CH3
(2R,3R) (2S,3S)

Net anti addition of bromine

 Br Br CH3 H Br
top + H H3C
H H +
CH
H3C b a H 3 H3C 1:1 Br CH3
Br
H CH3
Br2 Br− (a) (b)
H
H3C H
H CH3
H3C H
+
bottom
Br CH3 CH3
Br H H Br
Br H H Br
CH3 CH3
meso

Why bromonium bridge ion?

fulfill octet rule with extra bond formation

例 Br2
Br + Br
CCl4
Br Br

Anti addition of bromine

H + H
Br
※ Halohydrin formation

C C + X2 + H2O C C + HX
solvent X OH

(HO−X+) halohydrin

Mechanism:
:OH2
+
OH2 −H+ OH
+ X X +
X X X

Stereochemistry:
anti addition of X and OH
◎ Regiochemistry:

Br2
H2O HO Br

δ+ δ+
+
Br

More substituted C can stabilize positive charge more

has higher partial positive charge
※ Carbenes (碳烯)

Contain a divalent carbon, do not fulfill octet rule

 Highly reactive
例 H2C: (methylene)

 Structure:
empty p

R'
C
− R'
C sp3
R R
filled sp2
singlet carbene triplet carbene
(spin paired) (spin unpaired)
 Generation
◆ From diazomethane:

∆
H2C N N H2C: + N2
− +
or hν
methylene
diazomethane
(yellow color)
∆: heat (thermolysis)
hν: light (photolysis)

+ −
H2C N N H2C N N
− +

*Carcinogenic (致癌)
*Explosive
◆ From chlorofom: dichlorocarbene
Cl
t-BuOK
Cl C H Cl2C: + t-BuOH + KCl
Cl dichlorocarbene
chloroform
(pKa ~ 24)
an α-elimination
Cl −
OR
Cl C H
Cl
 Reaction
Addition to double bonds: formation of cyclopropanes

− C
H2
+ C
H2

例 Cl
t-BuOK
CHCl3 Cl 59%

7,7-dichlorobicyclo[4.1.0]heptane
◎ Carbenoids
carbene-like species

Simmons-Smith cyclopropanation:

CH2I2 + Zn(Cu) ICH2ZnI

a carbenoid

CH2I2/Zn(Cu)

Possible mechanism:
R R
H H R R
H H + ZnI2
I C ZnI
H2
Stereospecific syn-addition
※ Syn 1,2-dihydroxylation:
oxidation of alkenes
OH−
CH2=CH2 + KMnO4
cold HO OH
dilute
1,2-ethanediol
(ethylene glyol)

At higher T cleavage of diol occurs

1) OsO4
OH
2) Na2SO3 OH
or
NaHSO3/H2O
Mechanism:

OH−
O O + Mn(V)
−
O O 2e Mn H2O HO OH
oxidation −
Mn O O
O O− MnO2
(V)
(VII) a manganate ester (brown ppt)
purple

NaHSO3
O O + Oso
O O Os H2O HO OH
Os O O
O O
(VI)
(VIII)
*This mechanism is oversimplified
*OsO4 is highly toxic (it sublimes) and expensive
Stereochemistry: syn-addition of the two hydroxyl groups

cold dil. KMnO4 1) OsO4

OH−, H2O 2) NaHSO3

HO OH
cis
※ Oxidative cleavage by KMnO4

KMnO4, OH− O H+ O
CH3CH=CHCH3 2 CH3CO− 2 CH3COH
H2O, ∆

O O O O H O OH
Mn
O O− Mn(III)

(this mechanism is only to help your learning)

例 1) KMnO4, OH−
+ CO2 + H2O
∆ O
+
2) H
※ Ozonolysis

O O− O O O −
O
O+
O O
+
a carbonyl oxide
−
O
Zn, H2O O O+
O or O O
O O
Me2S
an ozonide
OH
O OH

hydrolyzes very easily

*When dimethyl sulfide (Me2S) is used in the reductive work-up,
Me2SO (dimethyl sulfoxide; DMSO) is the side-product
Overall:
R R'' 1) O3, CH2Cl2, −78 oC R R''
O O
R' H 2) Me2S R' H

A popular method for degradation

Preparation of aldehydes or ketones
Useful in structure determination
例 1) O3
+
O
2) Zn, H2O O
H
1) O3 H
O +
2) Zn, H2O O H
H
※ Halogenation of alkynes

Br Br2 Br Br
Br2
C C C C C C
CCl4 Br Br Br
anti-addition
possible to stop here
with 1 eq. of Br2

Same for Cl2

例 Br2 HO2C Br
HO2C C C CO2H C C
Br CO2H
※ Hydrohalogenation of alkynes
H Cl
HCl H HCl
C C C C C C
Cl H Cl

例 HCl H3C HCl

Cl
H3C C C H C CH2 H3C C CH3
Cl Cl
Markovnikov's
orientation

Mechanism: go through:
+
H−X H
R H R C C
R C C H C C H
X H
X− a vinyl cation
empty p
 H+
R H R H R H
R H + H H H +
+
X H X H X H
X H
resonance stabilized cation not so good

X−

R H
X H
X H
※ Oxidative cleavage of alkynes

1) O3 O O
R R' +
2) H2O R C OH HO C R'

1) KMnO4, OH− O O
R R' +
2) H+ R C OH HO C R'