Examples of

Electrocyclic Reaction
Woodward – Hofmann Rules for Electrocyclic Reactions:

Thermal() Photochemical(h)

4n conrotatory disrotatory

4n + 2 disrotatory conrotatory
 dis

(CH2)n (CH2)n n=0, = butadiene

n=1=
3 4

5
2
1
[2,1,0] bicyclo pent 2-ene
 Cl
OH
Br Solvolysis / HOAc
Br + Cl
dis rotation

(A) Cl -endo
Br - exo 1-bromo 7-hydroxy heptane

Br

Cl OH
Solvolysis / HOAc
Cl + Br
dis rotation
Cl -exo
(B) Br - endo

bicyclo [5,1,0] 7-chloro 1-chloro 7-hydroxy heptane

7-bromo heptane

epimers or diastereo isomers

The driving force in solvolysis is ring expansion of small membered ring

Endo group participates in solvolysis

OTs
OH

OH

disrotatory

ECRO
(CH2)4

Endo group participates in solvolysis

 Cl
OH
H
Solvolysis / HOAc

1250 C
(CH2)4

H
Cl
No reaction

even at 2100 C

This conclusively show the endo preference of

EC ring opening reaction
endo exo
Cl
Cl H
H Cl

 
No reaction up to 2500C

X X X

X=CH2, (CH2)n, N,O,S

Cl
Cl H

6
o
5 1  pyran

4 2

O O
3
dihydro pyran
6-chloro-3-oxa bicyclo Chloromones - colour of flowers & fruits
[3,1,0] hexane
o o
pyrone, oxo pyran
 Cl
Cl Cl
Cl


O O
6,6-dichloro-3-oxa Cl
Cl Cl
bicyclo[3,1,0]hexane
Cl


6,6-dichloro-bicyclo
Cl
[3,1,0]hexane
Cl Cl

Cl

below 00 C
5,5 dichloro bicyclo
[2,1,0] pentane

Ring strain is very high --- relief of ring strain plays key role
 (CH2)n

[n,1,0] bicyclo bicyclo [2,2,1] bicyclo [2,2,2]

alkane

(CH2)n m=4
n=3

trans
(CH2)n
cis bicyclo [4,3,0] nonane
cis bicyclo [m,n,0] alkane

n>m (CH2)m

(CH2)n
catenane
(m,n) pyrane
 Cl Cl

+ :CCl2
chloroform
& KOH

Cl H

carbebe insertion

:CHCl
o
o
DMF

An interesting extension of this type of reaction:

Cl
N -H+
dis N N
- Cl aromatisation

isoquinoline
4p systems are conrotatory under thermal condition

Butadiene Cyclobutene

 Con

 Con

thermal cleavage of cyclobutene to butadiene is preferred

the reverse reaction is not so favoured

h
 h

more favoured system

h
(CH2)n (CH2)n
 Cl
Cl
Con

Cl
Cl

trans -3,4- dichloro s-cis 1E,4E dichloro -1,3-butadiene

cyclobutene

H
Cl H
Con Cl

H
Cl H
Cl

cis -3,4- dichloro Z,E dichloro -butadiene

cyclobutene
 The reverse process is sometimes preferred
H
H
H H
H Con

800 C
H H H
H 100% H

s cis E,Z -1,3- cyclooctadiene [4,2,0]bicyclo octa-7-ene

It must be cis at fused points (can't be trans)

Cyclobutene is highly strained but when a 5 or 6 membered ring is fused to it, it gets
extra ordinary stability and resists to undergo ring cleavage.

X X
below 3800 C
 H Cl Cl

H H Cl

A B C

Dewar benzene
fused cyclobutene

B undergoes cleavage most easily

 H KJ/mol

A 96

Cl Cl

B 80

Cl Cl

C 127

Cl
Cl