ISSN : 2229-4944 (Print) IJEAR Vol.

3, Issue 1, Jan - June 2013

A Detailed Study on Pericyclic Reactions

1
Raj Kumar Pandey, 2Dr. Neelima Jain
CMJ University, Shillong, Meghalaya, India

Abstract result of a compounding of the long-established sigma designation

In organic chemistry, there exist Pericyclic reactions, stereochemistry
of which depends on symmetry of MOs (Molecular Orbitals) and
not on the overall symmetry of the molecules. So, in this paper,
we have done a detailed study on Pericyclic Reactions.
Keywords
Pericyclic Reactions, Molecular Orbits, Organic Chemistry, Stereo
Chemistry
from single carbon-carbon bonds and the Greek word tropos,
meaning turn. In this type of rearrangement reaction, a substituent
moves from one part of a -bonded system to another part in an
intramolecular reaction with simultaneous rearrangement of the
system. Fig. 3 shows Sigmatropic rearrangement.

I. Introduction
Pericyclic reactions are concerted reaction that proceeds via a
cyclic transition state having no distinct intermediates in the
reaction, in this type of reaction, Bond forming and bond breaking
steps are simultaneous but not necessarily synchronous [2]. Fig. 3: Sigmatropic rearrangement
There are various methods to analyze Pericyclic reactions. Some
of them are as follows: D. Group Transfer Reactions
Orbital symmetry correlation method (Woodward, Hoffmann, The concerted transfer of a group from one molecule to another
Longuet-Higgins and Abrahamson) due to concomitant movement of a -bond (from one molecule to
The frontier orbital method (Woodward, Hoffmann and another) and formation of a new -bond (between two molecules)
Fukui) at the expense of a -bond is generally referred to as group transfer
Transition state aromaticity method (Dewar and Zimmerman) Pericyclic reaction.
[1]

II. Types of Pericyclic Reactions

There are three types of Pericyclic reactions discussed below:

A. Electrocyclic Reaction
Formation of single bond between ends of a linear system or the
reverse process. Fig. 1 shows Electrocyclic Reaction. Fig. 4:

E. Cheletropic Reactions
Cheletropic reactions are a special class of cycloadditions or retro-
cycloadditions in which the two -bonds are either made or broken
to the same atom.

Fig. 1: Electrocyclic Reaction

B. Cycloaddition
Two or more unsaturated molecules (or parts of the same molecule)
combine with the formation of a cyclic adduct in which there is
a net reduction of the bond multiplicity. The resulting reaction
is a cyclization reaction. Many but not all cycloadditions are
concerted. Fig. 2 shows Cycloaddition.
Fig. 5:
F. Dyotropic Rearrangements
The pericyclic reactions which involve concerted intramolecular
migration of two -bonds simultaneously are known as dyotropic
rearrangements. However dyotropic reactions can also occur
stepwise.

Type 1:

Fig. 2: Cycloaddition

C. Sigmatropic Rearrangement
The net result is one -bond is changed to another -bond in an
uncatalyzed intramolecular process. The name sigmatropic is the Fig. 6: Two Migrating Groups Interchange Their Relative

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IJEAR Vol. 3, Issue 1, Jan - June 2013 ISSN : 2229-4944 (Print)

Positions Fig. 8: Molecular Orbitals

Type 2:
IV. Theories and Interpretation

A. Conservation of orbital symmetry (Woodward

Fig. 7: The -Bonds are Migrated to New Bonding Sites Without
any Positional Interchange for Groups [5].
Pericyclic Reactions have some rules known as symmetry rules
which are required and are discussed in Table 1.
Hoffmann)
This is the first theory that successfully explained and predicted
the outcome of Pericyclic reactions. It correlates all the relevant
orbitals in the starting material(s) and product(s).
B. Aromatic Transition State (Dewar-Zimmerman)
This is an easy concept to apply to all reaction types, but its not
so easy to understand why it is valid, especially in comparison
with the FMO approach that we will generally choose [4].

Table 1: Symmetry Rules for Pericyclic Reactions [7] V. Conclusion

Electron In 1950, two chemists, Otto Diels and Kurt Alder, discovered
Electron State Stereochemistry general method of preparing cyclohexene derivatives that is now
Pairs
known as the Diels-Alder reaction. The Diels-Alder reaction is one
Even Antara-con
type of a broader class of reactions that are known as pericyclic
Ground State number
reactions. Pericyclic reactions are the concerted reactions involving
Odd number Supra-dis
reorganization of electrons which occur by the way of a single
Even Supra-dis cyclic transition state.
Excited State number
Odd number Antara-con References
[1] S. Sankararaman,"Pericyclic Reactions", [Online] Available:
III. Frontier Molecular Orbital (FMO) http://www.nptel.iitm.ac.in/courses/IIT-MADRAS/
Frontier Molecular Orbital Theory was developed in the 1960s Engineering_Chemistry_III/pdf/5_Pericyclic%20reactions.
by Kenichi Fukui who recognized that chemical reactivity can pdf
often be explained in terms of interacting Highest Occupied [2] Eugen S. Andreiadis,"Stereochemical Aspects of Pericylclic
MOs (HOMOs), Lowest Unoccupied MOs (LUMOs) and Singly Reactions", May 2003, [Online] Available: http://www.
Occupied MOs (SOMOs). andreiadis.net/files/Andreiadis_Pericyclic-Reactions.pdf
[3] Pericyclic Reactions, [Online] Available: http://www.chem.
HOMO + LUMO Bonding MO purdue.edu/courses/chm651mal/Ch5_Pericyclic_Rxns.pdf
HOMO + HOMO Antibonding MO [4] Tim Wallace,"Pericyclic Reactions (CHEM30412)", [Online]
LUMO + LUMO Null interaction Available: http://www.personalpages.manchester.ac.uk/
SOMO + SOMO Bonding MO staff/T.Wallace/30412tw/PDFs/CHEM30412_TW_Lect1.
pdf
The FMO approach was developed by Woodward & Hoffmann [5] "Photochemistry and Pericyclic Reactions", National Open
in the late nineteen sixties who used it to explain an apparently University of Nigeria, [Online] Available: http://www.
diverse set of reactions involving -systems, including Diels-Alder nou.edu.ng/noun/NOUN_OCL/pdf/edited_pdf3/CHM%20
cycloaddition. Hoffmann used the approach to explore transition 414%20Photochemistry%20and%20Pericyclic%20
metal complexes [6]. Fig. 8 shows Molecular Orbitals. reactions.pdf
[6] Pericyclic Reaction Chemistry, [Online] Available: http://
www.fatih.edu.tr/~besat/Teaching/CHEM%20548/
Pericyclic%20Reaction%20Chemistry.pdf
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chem.psu.edu/chem39/Slides/Section11.pdf

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ISSN : 2229-4944 (Print) IJEAR Vol. 3, Issue 1, Jan - June 2013

Table 2: Comparison of Different types of Pericyclic Reactions [5]

Type Change in no. of bonds Change in no. of bonds Description
A cyclic product is formed;
Cycloaddition +2 -2 may be intermolecular or
intramolecular.

Electrocyclic +1 -1 Intramolecular

Intramolecular;
Sigmatropic 0 0 migration of a -bond;
rearrangement of -electrons

Intermolecular transfer of a group;

migration of a -bond from one
Group transfer +1 -1 molecule to another;
formation of new -bond at the
expense of one -bond.

A cyclic product is formed; two -bonds are formed

Cheletropic +2 -1 (-bond) -1 (lone pair)
to same atom; a lone pair is disappeared

dyotropic 0 0 Simultaneous migration of two -bonds

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