Sigmatropic Rearrangement Reactions

Sigmatropic rearrangements are another class of concerted pericyclic reactions governed by orbital
symmetry. This rearrangement involves a concerted reorganization of electrons during which a
group attached by a σ (sigma) bond migrates to the terminus of an adjacent π (pi) electron system.
The reactions are called sigmatropic rearrangement because a σ (sigma) bond appears to move
from one place to another during the reaction. There is a simultaneous shift of the π (pi) electrons.
The number of the π (pi) and σ (sigma) bonds remain separately unchanged.

Sigmatropic rearrangements are classified by a double numbering system (i, j or m, n) that refers to
the relative positions of the atom or group involved in the migration.
In a sigmatropic reaction, a σ bond migrates over a π system to a new position within the
system, either one end or both ends of the bond may move and the π systems becomes
reorganised in the process.

In which a group migrates with its sigma bond within a π-frame work is called a sigmatropic reaction.
Migration is accompanied by a shift in π-bonds.
An intramolecular migration of a group along conjugated π system is called sigmatropic
rearrangement. Basically, a sigma bond adjacent to conjugated π system is broken, the π
bonds reorganise and a new σ bond is formed at π system.

These reactions are classified according to no. of bonds separating the migration origin and
migration terminus in each component.
Migration of carbon takes place with the involvement of P orbital. P orbital has two lobes of
opposite phases.
Examples
In this representation 3 and 5 refers to the no. of migration terminus but ‘1’ does not
refers to the migration source, instead, it specifies that in both reactants and products
bonding is to the same atom ( no.1) in the migrating group.
Cope rearrangement is an example of sigmatropic rearrangement of order [3, 3]. Claisen
rearrangement is an another example.
Examples:
 In principle, the new bond could be formed on the same side or on the opposite face of the
π-frame work. These processes are termed suprafacial and antarafacial, respectively.
1. Addition of a σ bond is suprafacial if either retention or inversion occurs at both termini of
reacting σ bond.

2. Addition of σ bond is antarafacial if retention occurs at one end and inversion occurs at the
other end of the reacting σ bond.
Retention involves interaction of the head lobe of the σ bond with the other cycloaddition
component. Inversion involves interaction of the tail lobe of the σ bond with the other
cycloaddition component.
 Clearly suprafacial migration will usually be more feasible, geometrically also easily
accessible than antarafacial migration. Nevertheless, when the length of conjugated chain
becomes large enough, it becomes possible for a bond to migrate from the up face to the
bottom face of the conjugated system. Another point of interest is the inversion at the
migrating center. The option of inversion is not available to a H-atom. The inversion can be
experimentally observed or verified for asymmetric carbon. The ability of asymmetric to
invert leads to the four possible migration routes. They are,

❖ Suprafacial with retention

❖ Suprafacial with inversion

❖ Antarafacial with retention

❖ Antarafacial with inversion