CY-1-01(TO) :

Introduction to
Fundamental
and Applied
Chemistry
Sigmatropic Rearrangement

1
Sigmatropic Rearrangement

2
 stabilized by conjugation or the resulting double bond is more highly substituted, the equilibrium will be
2) the dienes are cyclic and ring strain is relieved; or 3) the Cope rearrangement is catalyzed by tran
the
4 formation of the [Link]
The reaction is bothReactions
stereospecific and stereoselective as a result of a c
The Cope
[Link] rearrangement of strained 1,2-divinyl cycloalkanes (cyclopropane and cyclob
state. The typical temperature required to induce Cope rearrangement in acyclic dienes is3 15
nvenient access
requiredto synthetically
temperature useful seven-
is significantly and
lower eight-membered
(room temp. or below)carbocycles.
when: 1) the dienes are substituted in 4
Cope C4; 2) the dienes are cyclic and ring strain is relieved; or 3) the Cope rearrangement is catalyzed
or Rearrangement
4
metal complexes. The Cope rearrangement of strained 1,2-divinyl cycloalkanes (cyclopropane and
2 2
gives convenient access to synthetically useful seven- and eight-membered carbocycles. 2
3 1
heat 3
2
1 (Z)
1
R 1
3
4 6 [3,3]
2 34 6 heat
2
5
R
3 1 4 5
heat6 3
[3,3] 1 (E)
R 6
5 R 4
2
4 6 4 6 [3,3]
5
(Z) 5 5 2
1 3
3 3 1
1 heat
heat 2
2
R (Z) 2
6 [3,3]
R (E) 3
1 2 6 3 [3,3]
(E) 12
4
3
1
R 4 heat 6 R 1 5
R 1 heat4
5 R 3 heat 3
4
6 [3,3] (E)
6 4 (E)
6 [3,3]
R 4
5 R 4 6 [3,3] 54 6
5 R R 5
5

(E) 2 2 3
1
R 1 3 1
heat 2 3 (E) 2 heat
2
R 29-43
R 1 (E) 1 Mechanism: 3 1
6 [3,3]3 4
heat 6 3
[3,3]
3 heat
R (E) 4 6
 29
cdubbed “no mechanism
rearrangements reactions”.
do not The Copeintermediates.
have observable rearrangement Therefore,
predominantlyin the
ate Rearrangement Reactions 29,32
bedwhere there is minimal steric interaction between the substituents. The
29
“no mechanism reactions”. The Cope rearrangement predominantly
depends on theissubstituents
where there and interaction
minimal steric varies between two extreme
between forms: from29,32
the substituents. twoThe
exane-1,4-diradical
Copethe depending on whether the bond making or bond breaking is
Rearrangement
ends on substituents and varies between two extreme forms: from two
reactions are concerted with a relatively late transition state where the bond
ane-1,4-diradical
d. depending on whether the bond making or bond breaking is
actions are concerted with a relatively late transition state where the bond
R R R
(Z)
R R R
R R * (E)R
meso chairlike TS (Z)
R R R
(E)
meso chairlike TS*
(Z)
R R R
(E)
R R R
racemic chairlike TS* (Z)
R R R
(E)
R R R
racemic chairlike TS*

4
 Rearrangement Reactions

Cope Rearrangement

5
 Rearrangement Reactions

Sigmatropic Rearrangements: Claisen Rearrangement

6
 Rearrangement Reactions

Sigmatropic Rearrangements: Claisen Rearrangement

7
 Rearrangement Reactions

Sigmatropic Rearrangements: Claisen Rearrangement

8
 Rearrangement Reactions

Sigmatropic Rearrangements: Claisen Rearrangement

9
Sigmatropic Rearrangement

10
Sigmatropic Rearrangement

11
Sigmatropic Rearrangement

12
Sigmatropic Rearrangement

13
Sigmatropic Rearrangement

14
Sigmatropic Rearrangement

15
Sigmatropic Rearrangement

16
Sigmatropic Rearrangement

17
Sigmatropic Rearrangement

18
Sigmatropic Rearrangement

19
Sigmatropic Rearrangement

20