 Electrocyclic Reaction

Part 4
Electrocyclic Reactions
 For example, let us consider electrocyclization of butadiene
and hexatriene systems.

Conrotatory And Disrotatory Modes

 In conrotatory mode, the two atomic orbital
components of the -bond may both rotate in the same direction,
clockwise or anticlockwise.
C2 = S

Conrotatory
Symmetric

 In disrotatory mode, the atomic orbitals may rotate

in opposite directions, one clockwise and the other
anticlockwise
m=S

Disrotatory
Symmetric

1
 Electrocyclic Reaction

Woodward-Hofmann
Selection Rule
No.of participating electron Stereochemistry
pairs ∆ hυ
Odd (1,3,5,..) Dis Con
Even (2,4,6,..) Con Dis

 Stereochemistry of electrocyclic reaction

Rotation Cis Trans
Conrotatory E,Z E,E
Disrotatory E,E E,Z
 Electrocyclic Reactions of Diene System

 Examples
h H3C CH3

Disrotatory
H H
Cis
H3C CH3
H H
Trans Trans C2 H3C H

Conrotatory
H H3C

Trans

2
 Electrocyclic Reaction
h H3C H

Disrotatory
H H3C

H CH3 Trans
CH3 H
Cis C2 H3C CH3
Trans
Conrotatory
H H
Cis

 Examples:-
H
H
h
1-
Disrotatory

H
H

h
H
2- Disrotatory
H

3
 Electrocyclic Reaction

 Another Examples:-
1- 
Con

h
Dis

Answer
CH3
H3C H

H3C C H3 Or
Conrotatory
H H
H C H3 CH3

trans-trans-2,4-hexadiene trans-3,4-dimethyl-cyclobutene

CH3
H3C C H3
h
H3C C H3 Or
Disrotatory
H H
H H CH3

trans-trans-2,4-hexadiene cis-3,4-dimethyl-cyclobutene

4
 Electrocyclic Reaction

2-
C H3
 h

C H3
Answer
H
H
CH3 H3C C H3
C H3
 Or
H Conrotatory
H H H
CH3
C H3
cis-trans-2,4-hexadiene cis-3,4-dimethyl-cyclobutene

Disrotatory h

H3C CH3
H H
trans-trans-2,4-hexadiene

5
 Electrocyclic Reaction

 Other Examples
H
H
h
1-
Disrotatory
O O
H
H
H
H
h
2-
Disrotatory

H
H

h
H
3- Disrotatory
H

6
 Electrocyclic Reaction
Important Example:-

h
conrotatory
ring opening

HO
Ergosterol

1
H h
1
7 [1,7]H migration

2
6

3 5
HO
4

HO
Vitamin D

7
 Electrocyclic Reaction
 Electrocyclic Reactions of Triene System
 Disrotatory
h Conrotatory

Example:-


Dis
Dis
a) b)
h
h
Con
Con
Answer
C H3
a) E
C H3 
Dis C H3
H
Cis
H
C H3
E C H3 h
Con
C H3
Trans

C H3
b) Z
H 
Dis C H3
C H3
Trans
H
C H3
E C H3 h
Con
C H3
Cis