Types of Rearrangements

Rearrangements are divided into intramolecular and

intermolecular processes.

In intramolecular process, the group that migrates is

not completely detached from the system in which
rearrangement is taking place.

In contrast, in intermolecular process, the migrating

group is first detached and later re-attached at another
site.
1. Rearrangement to Electron Deficient Carbon
a. Wagner-Meerwein Rearrangement
b. Pinacol Rearrangement

2. Rearrangement to Electron Deficient Nitrogen

Beckmann Rearrangement

3. Rearrangement to Electron Deficient Oxygen

Baeyer-Villiger Reaction

4. Rearrangement to Electron-Rich Carbon

a. Favorskii Rearrangement
b. Wittig Rearrangement

5. Aromatic Rearrangements
a. Fries Rearrangement
b. Claisen Rearrangement
 1. Rearrangement to Electron Deficient Carbon
a. Wagner-Meerwein Rearrangement

CH3 + CH3
H
CH3 C CH2OH CH3 C CH2OH2
CH3 CH3 H2O
- Cl
Cl
CH3 CH3 C CH2CH3
CH3 C CH2 CH3 C CH2CH3 CH3
CH3 CH3 H+ CH3C=CHCH3
CH3
OH H+ + +

Secondary Tertiary
carbocation carbocation
 CH3 CH3
CH3 C CHCH3 SN1 CH3 C CHCH3
CH3 Br CH3
CH3 C CHCH3 Product
CH3 CH3
Stable cation

CH3 CH3
CH3 C CHPh SN1 CH3 C CHPh
CH3 C CHPh
CH3 Br CH3 CH3 CH3

Stable cation
Product
CH2NH2
CH2+ H2O
CH2OH
HNO2 +
H
N2 32%
H+

+
H+ H2O OH
H+
2% 58%
1. Rearrangement to Electron Deficient Carbon
b. Pinacol Rearrangement

Conversion of substituted 1,2-diols to

ketone/aldehyde

1,2-diols ketone

1,2-diols
aldehyde
Mechanism:

CH3 CH3 H+ CH3 CH3

CH3 C C CH3 CH3 C C CH3
H2O
OH OH OH +OH2

CH3
CH3 CH3
+
CH3 C C CH3 CH3 C C CH3 CH3 C C CH3
+
OH CH3 +OH CH3
H
O CH3
Pinacol rearrangement is regioselective: major product is
based on more stable carbocation

The stable cation formed superior

+
Ph2C CH2 H Ph2C
+
CH2
OH OH OH
Ph2CH CH Ph2CH CH
+
+OH H
O
Phenyl group move first

H+
PhHC CHPh PhHC CHPh
+
OH OH OH
Ph2CH CH + Ph2CH CH
+OH H
O
 Phenyl with electron donor group move first

(p MeOC6H4)2C CPh 72%

+
H Ph O
(p MeOC6H4)2C CPh2
OH OH
p MeOC6H4C CPh2 28%
O C6H4OMe p
Under HNO2, the amino alcohol rearranges
under pinacol
2. Rearrangement to Electron Deficient Nitrogen
Beckmann Rearrangement

inserts in anti
bond
3. Rearrangement to Electron Deficient Oxygen
Baeyer-Villiger Reaction

17
 O CH2Cl2
O
CH3 C Ph CF 3CO3H CH3 C OPh

O O
CH3COOEt
CF 3CO3H O
4. Rearrangement to Electron-Rich Carbon
a. Favorskii Rearrangement

O O
C C R KOH C C OH
Cl R

O O
(CH3)2C C CH3 NaOEt (CH3)2C C OEt
EtOH
Br CH3

O O
Ph2C C CH3 NaOEt Ph2CCH2 C OEt
EtOH
Br
Mechanism of Favorskii Rearrangement
O O
H C Cl RO- C Cl -
Cl
C C ROH C C

O -
RO O
C - C
C C RO
C C

RO RO O
O
C ROH C
C C C C H
For asymmetric cycloprapanone, the
stable anion form dominantly
O RO O-
- PhCH CH2COOR
RO
Ph Ph stable carbon anion

RO - COOR
O
PhCH CH2
Ph
relative unstable carbon anion
Different α- chloroketone form same
rearrangement product:

O O
PhCH2 C CH2 -
Cl RO
O ROH Ph
PhCH C CH3
Cl
PhCH2 CH2COOR
Intramolecular SN2 attack (structure
maintaining):
Me Me Me
Me
O
COCH3 O - OH H+
COOH

H KOH HO H H
H -
Cl CH2 Me

Me
Me Me Me
Cl -
KOH - CH2 H+
Me
H HO H
H H
COCH3 OH COOH
O
O
4. Rearrangement to Electron-Rich Carbon
b. Wittig Rearrangement

PhCH2 CH3 PhLi PhCH CH

3
+
O H O
H+
PhCH CH3 PhCH CH3
O OH
CH2=CHCH2 CH2=CHCH OH
NaNH2
O CH2=CHCH2
CH2=CHCH2 liq NH3
 5. Aromatic Rearrangements
a. Fries Rearrangement

The Fries Rearrangement enables the preparation of acyl

phenols.
Mechanism of the Fries Rearrangement

acylium ion

acyl phenol
 OH
COCH3

CH3 80-85%

OH

CH3 95%
COCH3
 5. Aromatic Rearrangements
b. Claisen Rearrangement

Intramolecular Migration from Oxygen to Carbon

Rearrangement of phenyl allyl ether to allylphenol

OH
O OH

+

[3,3]-sigmatropic rearrangement
OH
O OH

+

OH

O O

OH
O O
H

tautomerisation

H
chair transition state
boat transition