Alcohols

Part 1

Alcohol reaction map

5. Addition of Water to Alkenes:

Acid-Catalyzed Hydration

Overall process
Addition of HOH across a C=C bond
H+ is the electrophile
Follow Markovnikovs rule

H2O

Ch. 8 - 3

dilute H3O+
(e.g. dilute H
2SO4, H3PO4)

OH

5A.

Mechanism

H
H

H2O

slow

fast
(step 2)

(step 1)

more stable

3o cation
fast
(step 3)

H2O

H
H
Ch. 8 - 4

H
H

+
OH

5B. Rearrangements

Rearrangement can occur with certain

carbocations
H2O

H2SO4

1,2-alkyl shift

NOT
OH

Ch. 8 - 5

OH

(major product)

H2O

 Oxy-mercuration-demercuration

Mechanism

Stereospecificity

Regioselectivity

6B. Rearrangements Seldom Occur in

OxymercurationDemercuration

Recall: acid-catalyzed hydration of some alkenes leads to

rearrangement products

e.g.
H2O
H2SO4

Ch. 8 - 10

OH
H

H2O
H2SO4

1,2-alkyl shift
H

H
H

H2O
OH
H
Ch. 8 - 11

H2O

Rearrangements of the carbon skeleton seldom occur in

oxymercurationdemercuration

no rearrangement
OH
1. Hg(OAc)2, THF-H2O
2. NaBH4

via

Ch. 8 - 12

H
OH

Hg(OAc)

4A. Alcohols from Alkyl Hydrogen

Sulfates

conc. H2SO4
cold

OSO3H
H

OH

H2O
heat

The overall result of the addition of sulfuric acid to an alkene

followed by hydrolysis is the Markovnikov addition of H

Ch. 8 - 13

and OH

4. Addition of Sulfuric Acid to Alkenes

OSO3H

conc. H2SO4
cold

O
HO

O H

OSO3H

more stable
3o cation

Addition of HOSO3H across a C=C bond

Ch. 8 - 14

less stable
1o cation

Hydroboration oxidation

Examples

8A. Mechanism of Hydroboration

H3C
H
H

H3C
H

H
+
B

H3C

H
B

H3C

H
H

H
H

H
complex

H
H

H3C
H

H
B H
syn addition
H
ofCh.H
and B
8 - 17

four-atom
concerted T.S.

B H
H

Other examples

(1)

BH2-THF

+
H

BH2
(99

(2)

BH2-THF

1)

+
H

BH2
(98

Ch. 8 - 18

H2B

H2B
:

2)

8B. Stereochemistry of
Hydroboration

Syn addition

H3C

Ch. 8 - 19

BH3-THF

BH2

CH3

9. Oxidation and Hydrolysis of

Alkylboranes

H
H

Ch. 8 - 20

BH2

B always ends
up on the least
hindered carbon

B H

B
H

(trialkyl borane)

Oxidation

Ch. 8 - 21

H2O2
O

Via

R
R3B

OH

OH

R
R

HO O

RO

R
OR

R
O
HO
Ch. 8 - 22

B
OR

O
OR

OR

RO

OR

OR
OH

OR

OH

Hydrolysis

O
O

NaOH
H2O

3
Ch. 8 - 23

OH + Na3BO3

Overall synthetic process of hydroboration-oxidation-hydrolysis

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

Ch. 8 - 24

OH

Overall: anti-Markovnikov addition of HOH across a C=C bond

Opposite regioisomers as oxymercuration-demercuration

anti-Markovnikov
syn addition

Example

BH3-THF
H3C

H
H

OH

CH3

This oxidation step occurs with retention of

configuration
Ch. 8 - 25

BH2

CH3

H
H2O2
OH

10.Summary of Alkene Hydration

Methods
Summary of Methods for Converting Alkene to
Alcohol
Reaction

Regiochemistr
y

Occurrence of
Stereochemistr Rearrangemen
y
ts

Acid-catalyzed
hydration

Markovnikov
addition

Not controlled

Frequent

Oxymercuratio
ndemercuration

Markovnikov
addition

Not controlled

Seldom

Stereospecific:
syn addition of
H and OH

Seldom

Hydroboration- Antioxidation
Markovnikov
addition
Ch. 8 - 26

Examples
via

H
H

OH

1,2-hydride
shift

with
H
rearrangeme
nt

H2O

OH

1. Hg(OAc)2, THF-H2O

2. NaBH4, OH

1. BH3-THF
Ch. 8 - 27

2. H2O2, OH

Markovnikov addition of
H2O without
rearrangement
H
antiOH Markovnikov, syn
addition of

11.Protonolysis of Alkylboranes
R

alkylborane

CH3CO2H
heat

H + CH3CO2

alkane

Protonolysis of an alkylborane takes

place with retention of configuration;
hydrogen replaces boron where it
stands in the alkylborane
Overall stereochemistry of
hydroborationprotonolysis: syn

Ch. 8 - 28

Fleming-Tamao Oxidation

Tamao-Kumada Oxidation

Mechanism

Grignard mediated alcohol synthesis