THE PERICYCLIC REACTIONS

Delivered by: Ayesha Aftab

Introduction
Definition:
“A pericyclic reaction is the type of organic reaction wherein the transition state of the molecule has a cyclic
geometry, the reaction progresses in a concerted fashion, and the bond orbitals involved in the reaction
overlap in a continuous cycle at the transition state.”

May also be defined as:

“ Any concerted reaction in which bonds are formed or broken in a cyclic transition state i.e electrons move around
in a circle.”
❖ A concerted reaction is a chemical reaction in which all bond breaking and bond making occurs in a
single step. Reactive intermediates or other unstable high energy intermediates are not involved
There is a single transition state from start to finish, in contrast to a stepwise reaction.
There are numerous reactions in organic chemistry that proceed through cyclic transition states.
General Features
Pericyclic reactions require light or heat and are completely stereospecific that is, a single
stereoisomer of the reactant forms a single stereoisomer of the product.

Pericyclic reactivity can be understood in terms of frontier molecular orbital (FMO) theory
and the outcome of the reaction can be predicted using the Woodward-Hoffmann rules.

Properties of Pericyclic Reactions

a) Little, if any, solvent effect.
b) No nucleophiles or electrophiles involved.
c) Not generally catalyzed by lewis acids.
d) Highly stereospecific.
e) Often photochemically promoted.
Examples
❖ An important and familiar example is the Diels-Alder reaction, in which a conjugated diene cyclo adds to an
alkene or alkyne:

This reaction is an example of a [4 + 2] cycloaddition. Such reactions occur thermally (by simply heating the
reactants) and appear to be entirely concerted. By this it means that the reactants are converted to products in one
step, without involving the formation of reaction intermediates.

❖ Epoxidation of alkenes occurs through concerted transition state, the reaction is completely stereoselective
due to the absence of intermediates.
Pericyclic Reactions in Biological Systems
CLASSIFICATION OF
PERICYCLIC REACTIONS

DELIVERED BY:
MAH AROOJ SAJID
 CLASSIFICATIONS

1. Cycloaddition reaction
2. Electrocyclic reaction
3. Sigmatropic rearrangements
4. Cheletropic reaction
5. Group Transfer
 CYCLOADDITION REACTION
● A cycloaddition is a chemical reaction in which two or more unsaturated
molecules (or parts of the same molecule) combine with the formation of a
cyclic adduct .
▪  Many but not all cycloadditions are concerted and thus pericyclic. Non-
concerted cycloadditions are not pericyclic.
 ELECTROCYCLIC REACTION
● An electrocyclic reaction is a type of pericyclic reaction where the net result
is one pi bond being converted into one sigma bond or vice versa.
● Reactions can be either photochemical or thermal.
● Reactions can be either ring-opening or ring-closing .
. A classic example is the thermal ring-opening reaction of 3,4-
dimethylcyclobutene.
 SIGMATROPIC REARRANGEMENT

● A sigmatropic reaction in organic chemistry is a pericyclic reaction wherein

the net result is one σ-bond is changed to another σ-bond in an
uncatalyzed intramolecular reaction.
● Example
● The ortho-Claisen rearrangement involves the [3,3] shift of an allyl phenyl
ether to an intermediate which quickly tautomerizes to an ortho-
substituted phenol.
 CHELETROPIC REACTION

● It is a specific type of cycloaddition , wheres the two bonds are made or

broken at the same atom.
 GROUP TRANSFER

● A group transfer reaction is a pericyclic process where one or more

groups of atoms is transferred from one molecule to another. 
o Unlike other pericylic reaction classes, group transfer reactions do not have
a specific conversion of pi bonds into sigma bonds or vice versa.
o The best known group transfer reaction is the ene reaction in which an
allylic hydrogen is transferred to an alkene.