Sigmatropic Rearrangements

Involve concerted migration of a σ-bond across a conjugated

π-system

Represented as [i,j]
i = number of atoms in the migrating fragment

j = number of atoms in the π system

(Species directly involved in the bonding changes)

 2 2
1 3 1 3
[1,3]
R R

[1,5]
* *
R R

[1,7]
CH 3 H 3C *
*

R S O
[2,3]
S O
R
 Δ

[3,3]
Cope rearrangement

Δ

[3,3]
Claisen rearrangement
 Name this shift

Name this shift

 H

supra

antara
 H

antara

What about 1,3 shift under

Photochemical conditions?
 Does not involve radicals;
It is considered just for orbital analysis

[3,3] X X X
Y Y Y
Cope Rearrangement: Boat vs. Chair Transition State

H H
Me trans-trans
Me 90%
Me H Me
H
Me Me
H cis-cis 10%
H H
H Me
Me
Me H
Me H H trans-cis <1%
H Me Me

Me Me

Me trans-cis 99.7%
H Me
H
H H
Me Me
Me H Me trans-trans 0.3%
H H H
 H
Cope 5-20°C

Degenerate Cope Systems

 Oxy-Cope

H
220°C keq ~ 105

OH OH O

Anionic Oxy-Cope
Potassium, TBA X increases rate by factors of 1010-10-17!; can work at low temps.
Water elimination at high tem. in oxy cope can be avoided

OX

OX 66°C H

THF H
MeO

OMe
Claisen Rearrangement

O O O OH
heat
R R R R
H

If both orthopositions are blocked, second [3,3] sigmatropic shift happens

O OH
O O
R R R R
R R R R
Cope

H
 Et
O
Via Chair intermediate:
O
144°C Et
O

t-Bu t-Bu

t-Bu diastereoselection >87:13

O
EtO
O OEt
O
OEt
t-Bu t-Bu
t-Bu
ratio 52:48
 [1,7] antara

In cyclic systems, antara shift is unlikely due to

steric reasons; in open system, it can happen