Dr.

Sana Aslam
Assistant Professor
Department of Chemistry
Government College Women University
Faisalabad

M.Phil . 2nd Semester

Course Code: CHM-732
Course Title: Pericyclic Reactions
Contents
•Sigmatropic Rearrangements
•[1,3]-Sigmatropic Rearrangements
•[1,5]-Sigmatropic Hydrogen Shifts
•[1,7]-Sigmatropic Hydrogen Shifts
•[3,3]-Sigmatropic Rearrangements
•[2,3]-Sigmatropic Rearrangements
KEY POINT
•In a sigmatropic rearrangement, a  σ bond in the reactant is broken, a new σ bond
is formed, and the π electrons rearrange. The σ bond that breaks is a bond to an allylic
carbon.
•“Sigmatropic” comes from the Greek word tropos, which means “change,” so
sigmatropic means “sigma-change.”

•In a sigmatropic reaction a σ bond 'migrates' across a conjugated system to a new site.
•If '[n,m] sigmatropic rearrangement' has n = 1, then one end of the bond that moves
remains attached to its original atom — the n refers to the fact that the other end of the
bond migrates across n atoms. This type of reaction often features a migrating C–H
bond, i.e. a [1,n] hydrogen shift.

•True sigmatropic reactions are usually uncatalyzed, although Lewis acid catalysis is
possible. Sigmatropic reactions often have transition-metal catalysts that form
intermediates in analogous reactions. The most well-known of the sigmatropic
rearrangements are the [3,3] Cope rearrangement, Claisen rearrangement, Carroll
rearrangement and the Fischer indole synthesis.
•Sigmatropic rearrangements have cyclic transition states. If
the transition state has six or fewer atoms in the ring,
rearrangement must be suprafacial because of the geometric
constraints of small rings.

•They are all concerted reactions. This means that all the
electron reorganization takes place in a single step.
Therefore, there is one transition state and no intermediate.

•Because the reactions are concerted, they are highly

stereoselective.
•The symmetry rules for sigmatropic rearrangements are
nearly the same as those for cycloaddition reactions.
Numbering System of Sigmatropic Rearrangement

The numbering system used to describe a sigmatropic rearrangement.

First, mentally break the σ bond in the reactant and label both atoms that were
attached by the bond a s number 1.
Then look at the new σ bond in the product. Count the number of atoms in
each of the fragments that connect the broken σ bond and the new σ bond.
The two numbers are put in brackets with the smaller number stated first.
Typical reactions
[1,3] Sigmatropic rearrangement
A [1,3] sigmatropic rearrangement involves a π bond and a pair of σ electrons(two
pairs of electrons).
[1,5] Sigmatropic rearrangement
A [1,5] sigmatropic rearrangement involves two π bonds and a pair of σ electrons
(three pairs of electrons).
[1,7] Sigmatropic rearrangement
A [1,7] sigmatropic rearrangement involves four pairs of electrons.
[2,3] Sigmatropic rearrangement
[3,3] Sigmatropic rearrangement
Most synthetically useful sigmatropic rearrangements are two- or six-electron
processes.
The [3,3] sigmatropic rearrangements (Cope and Claisen rearrangements) are the
most widely used sigmatropic rearrangements.
A Cope rearrangement is a [3,3] sigmatropic rearrangement of a 1,5-diene.
A Claisen rearrangement is a [3,3] sigmatropic rearrangement of an allyl vinyl
ether.
Both rearrangements form six-membered-ring transition states. The reactions,
therefore, must be able to take place by a suprafacial pathway.
*[1,5] Sigmatropic migrations of hydrogen are well known. They involve three pairs
of electrons, so they take place by a suprafacial pathway under thermal conditions.
A concerted [1,7] shift of hydrogen is thermally allowed if it can reach the
opposite face of the π system antarafacially, which is possible via a helical
conformation. [1,7] Sigmatropic hydrogen migrations involve four pairs of
electrons. They can take place under thermal conditions because the eight-
membered-ring transition state allows the required antarafacial
rearrangement.