UNIT 12 PERICYCLIC REACTIONS

Structure
12.1 Introduction
Objectives

12.2 Pericyclic Reactions

Classification

12.3 Theoretical Basis of Pericyclic Reactions

Molecular Orbital Theory
Molecular Orbitals of Conjugated Polyenes

12.4 Cycloaddition Reactions

[2+2] Cycloadditions
[4+2] Cycloadditions

12.5 Electrocyclic Reactions

Cyclisation of 4n Systems
Cyclisation of (4n+2)Systems

12.6 Sigmatropic Rearrangements

Classification of SigmatropicRearrangements
Mechanism
12.7 Summary
12.8 Terminal Questions
'

12.9 Answers

12.1 INTRODUC TION

Most of the organic reactions you have studied so far proceed stepwise, exceptions being
the S, 2 and E2 type of reactions. A large number of reactions of conjugated polyenes,
however, proceed by concerted mechanisms, i.e., the old bonds are broken and the new
ones formed in a single concerted step. These reactions are called pericyclic reactions,
they are characterised by a cyclic transition state involving sigma or pi-bonds. Pericyclic
reactions are initiated by heat or light and are highly stereospecific. In this unit we will
discuss these reactions.

Objectives

After studying this unit you should be able to:

define pericyclic reactions and describe their bmad characteristics,

classify pericyclic reactions into cyclo-addition reactions, electmcyclic reactions and

sigmatropic rearrangementsand

explain the mechanism of these reactions using the frontier orbital method.

PERICYCLIC REACTIONS
Pericyclic reactions are concerted reactions. They are characterised by the making or
breaking of bonds in a single concerted step through a cyclic transition state involving x or
a electrons. Energy of activation for pericyclic reactions is supplied by heat in a
Reaclbn Interaedhtes and reactions are highly stereospecific, often the thermal and photochemical processes yield
Molecuhr Rearrangemcnb products with different but specific stereochemistry. Since pericyclic peactions d o not
involve ionic o r free radical intermediates, solvents. and nucleophilic o r electrophilic
reagents have no effect on the course of these reactions.

There are three principal types of pericyclic reactions.

1) Cycloaddition reactions: in which two molecules combine to form a ring; two x

bonds being converted to two sigma bonds in the process. The best known example of
a cycloaddition reactions is the Diels-Alder reaction shown below.

1,3-butadiene ethene cyclohexene

2) Electrocyclic reactions are reversible reactions in which a compound with

conjugated double bonds undergoes cyclisation. In this process two pi electrons are
used to form a sigma bond.

3) Sigmatropic rearrangements are concerted intramolecular rearrangements in which

an atom o r a gtoup of atoms shifts from one position to another.

12.3 THEORETICAL BASIS OF PERTCYCLIC

REACTIONS
A theoretical understanding of pericyclic reactions had eluded chemists for many years.
However, since 1%0 several theories have been proposed to give a rational explanation of
these reactions. Woodward and Hoffmann have proposed the principle of conservation of
orbital symmetry as the theoretical basis for explaining these reactions. Fukui has used
the frontier orbital method. We will use the latter here for studying pericyclic reactions.
Before we discuss the mechanism of these reactions, it would be better to recapitulate
salient features of the molecular orbital theory.

12.3.1 Molecular Orbital Theory

According to the molecular orbital theory, molecular orbitals are formed by linear
combination of atomic orbitals (LCAO). For example when a molecule of hydrogen is
formed from two atoms of hydrogen, the atomic orbitals are supposed to combine to give a
bonding orbital which is lower in energy than the separate atomic orbitals. In addition, an
antibonding orbital is also supposed to exist, which as its name implies does not contribute
to the bond formation between the atoms. a * is higher in energy than a orbital or the
individual atomic orbitals.
antibonding orbital of Hz

bonding orbital of Hz
82
 m e bonding molecular orbital is supposed to arise from reinforcement of in-phase
s-atomic orbitals, whereas the antibonding molecular orbital arises from interference
P ~ c U C --
RB. woodward of I-iarvani
Univenity got Nobet prize in 1965
for his work on the synthesis of
between the out-of-phases-atomic orbitals. This% shown diagramatically in Fig. 12.1. complex organic compounds
including chlorophyll.

R.Hoffman of Cornell University

and K Fukui of Kyoto Univenlty
shared the 1981Nobei prize for their
under sunding of pericylic r u e t i o ~

out of phase
potential
energy, E

h~ghe dens~ty

Fig. 12.1 : Bonding and antibondhg orbllnk of hydrogen mokcular

As you know, in saturated hydrocarbons like methane or ethane carbon atoms are sp3
hybridised and there are sigma bonds between carbon atoms as well as between carbon and
hydrogen atoms formed by the overlap of s]~'-sp' or s$-s atomic orbitals. Each of these
sigma bonds will have a bonding orbital and the corresponding antibonding orbital.

However, hybridisation of carbon atoms becomes different in an alkene like ethene. Here
I
the carbon atoms are supposed to be sp2hybridised. The double bond between the two
I carbon atoms is supposed -9 comprise of a a and a n bond. The carbon-carbon a bond is
I
formed by the overlap of twos# orbitals, resulting in a bonding orbital and an antibonding
orbital. The n bond is formed by the sideways overlap ofp-orbitals resulting in two n -

TI* antibonding orbital

HI bonding orbital
Fig. 12.2 :%,,andr.,*o r b l b b otetNnc
Rtaclbn InttnntdLkr and Fig. 12.2 shows the representalion of n,and n,* orbitals of ethene. Note that n, * ,which is
MokcuLr ReamngcmtnU formed by interference between the out-of-phasep-orbitals has a node o r a region of
minimum electron density between the nuclei. x,* Orbital is of higher energy than x,.The
following diagram compares the energies of a,a*,x, and x,* orbitals. As expected the
bonding electrons are in the two orbitals with lowest energies, a and x, in the ground state
of ethene.

Ground d.@otC=C h tlhtnt

As you can see a orbital is of higher energy than x,*.The amount of energy required to
promote an electron from a to a*orbital is greater than that required to promote a x
electron to x* orbital. Because of the large amount of energy required to promote a sigma
electron, electron transitions of this types are rare and therefore unimportant to the organic
chemist. However, x + n* transitions, which require less energy, are important. In Ihe
reactions discussed in this unit, you will come across examples of such transitions.

12.3.2 Molecular Orbitals of Coqjugated Polyenes

After this brief description of bonding and antibonding molecular orbitals, let us study
some features of the molecular orbitals of conjugated polyenes. A conjugated polyene
contains either 4n or (4nt2) pi electrons in its conjugated system. n is an integer and the
simplest 4n system is represented by 19-butadiene where n=1. Any conjugated diene
contains n molecular orbitals similar to those of 13-butadiene. We can, therefore, use 1.3-
butadiene as a model for all conjugated dienes.

In 1,3 -butadiene, fourp-orbitals are used in the formation of the x molecular orbitals, Ihus
four n molecular orbitals result. Of these x, and x, are bonding orbitals and x,* and x,*
are antibonding orbitals. Fig. 12.3 depicts these orbitals in terms of increasing energy. As
you can see higher energy orbitals are associated with greater number of nodes.

(3 nodal planes: all f o u r p

orbitals out of phase)

IF+
-- --
2 (1 nodal plane)

1E
(no nodal planes between
C nuclei; all four p orbitals
"1
in phase)

Flpm 123 :Tbe bondhg and a n t h n d h g x w k c u h r orbitalp ot 1J-butadkn.

In the ground state of butadiene, the four x electrons are in the two orbitals of lowest
energy n, and x, In this case
 Pcrkpclle ~ c a c W m We can now discuss the mechanism of pericyclic reactions, but before that try the

Draw the orbital diagram for the lowest energy excited state of 1,3,5-hexatriene.

............................................................................................................................................

12.4 CYCLOADDITION REACTIONS

As said earlier, in a cycloaddition reaction two unsaturated molecules undergo an addition

reaction to yield a cyclic product. For example, cyclisation of ethene to cyclobutane on

The cycloaddition of ethene or any two simple alkenes is called a [2+2] cycloaddition as
two pi electrons t two pi electrons are involved. The Diels-Alder reaction shown below is
an example of a [4+2] cycloaddition. The diene here contains four x electrons and the
dienophile two. The carbonyl pi electrons which are not used in bond formation in the
reaction are not included in the number classification of this cycloaddition.

CHO CHO

diene dienophile
4 n electrons 2 n electrons

I
Cycloaddition reaction are concerted, stereospecific reactions. Any particular reaction is
either thermal or photo-induced but not both. Let us try to analyse these reactions in terms
of frontier orbital theory.

I 12.4.1 r2+21Cvcloadditions

explained by assuming that' the electrons "flow" from the HOMO of one molecule to
LUMO of the other. For this the HOMO of one molecule must overlap with the LUMO of
the second molecule. It cannot overlap with HOMO of the second molecule because this
orbital is already occupied. Simultaneouslywith the merging of the x orbitals, these
orbitals undergo rehybridisation to yield new sp' sigma bonds.
Let us consider [2+2] cycloaddition of ethene to give cyclobutane. As discussed above
ethene has two n molecular orbitals n, and n2*.In the ground state n, is the bonding
orbital and the HOMO while n2* is the antibonding orbital and LUMO.

A n2 1- -
-
LUMO

5-1 T
I
- HOMO

When ethene h heated, n electrons are not promoted but remain in the ground state. If you
examine the phases of the ground state HOMO of ethene molecule and the LUMO of
another ethene molecule, you can see why cyclisation does not occur by thermal induction.

- no r e a c t i o n

For bonding to occur, the phases of the overlapping orbitah HOMO of one molecule and
LUMO of the other molecule must be the same. This is not the case in the g r o u ~ dstate
HOMO and L U M of ~ two ethene or any [2+2] system. Because tne phases of the orbitals
are incorrect for bonding, a thermally induced [2+2] cycloaddition is said to be a
iymmetry-forbidden reaction.

When ethene is irradiated with ultraviolet light, a x electron is promoted from n, to x,*
orbital in some, but not al! molecules. This results in a inixturl o l the gror~ndstate and
excited state ethenc molecules. Now, if you examine [lie HOMO of an excited molecule
and the LUMO of a ground state molecule you can see that tile phases are correct for
bonding. Such a reaction has a relatively low energy of activation and is said to be
symmetry-allowed.

phases correct for bonding

symmetry allowed ground LUMO, rr; transition state
to which n orbitals
are being rehybri-
dized to o orbitals
*

In general, thermally induced [2+2] cycloadditions are symmetry forbidden and photo-
induced [2+2] cycloadditions are symmetry allowed. A symmetry forbidden reaction may
take place under differenr cpnditions, but then the energy of activation is very high. This
will not be a cen,*r:ted reaction and may proceed stepwise through radical intermediate.

12.4.2 [4+2] Cycloadditions .

The thermal [4+2] cycloaddition has been known for almost half a century as the Diels-
Alder reaction. It has proved synthetically useful since it unites two carbon skeletons
smoothly and stereospecifically. In Diels-Alder reaction, a six membered ring is formed by
1,4-addition of an olefinic unit to a conjugated diene. Diels Alder is a cis or syn addition,
the diene must have S-cis conformation.
 S-oia diene crb dienophile

coOrom'nOO~
a-
are
-1~rmrdo0r d 13- (irmdbOr
-
tetramethylbutadiencs, atedc hindrance dcctcascs activity. The dienophile is adivated by
-
electron-withdrawing substituents like- COOH, COOR, CHO, COR, CN, -
--NO, etc. %me reactive dienes do not need adivation as is illustrated by the
-
dimerisation of cvclo~cntadiene.

latter is induced the&ally. To see why this is so, we w&ld have to examine the HOMO-
LUMO interactions of thcp-orbitals that will form new sigma bonds in [4+2]
cycloaddition. Let us first compare the HOMO-LUMO interactions for the ground state for
a thermally induced reaiiion. We will use the simplest [4+2] system, the cycloaddition of
1,3-butadiene and ethene. In the thermally induced cycloaddition between these two
mctants, we can visualise the pi electrons flowing from HOMO, n, of the diene (Fig.
123) to the LUMO $, of the dienophile. You can see that orbitals that lead to
cvcloaddition are in phtse. The mction therefore is symmetry allowed.

cannot &erGp with the LUMO of the dierkphile be&& thetwo are not in-phase. 'Ihe
photo induced [4+2] cylisation, therefore, is symmetry-forbidden.

1 eymmetry forbidden

(a) Explain why in [4+2] cycloaddition, diene is activated by electron donor substituents
and dienophile by electron-withdrawing substituents.
@) Predict whether a photo induced [4+2] cycloaddition would be possible if the
dienophile instead of the diene were the excited reactant.
Rc.e(bn Intcnnedhk . a ways in which the existing C--C sigma bonds can rotate in order to bring thep-orbitals in
~ o k u h Rearnngemenls
r phase for overlap.

The two C- C sigma bonds can rotate in the same direction, either both clockwise or
both counter-clockwise. This type of rotation is called conrotatory.

The two C- C sigma bonds can rotate in the oppasite directions, one clockwise and
the other anticlockwise. fiis type of rotation is called disrogtory.

fi both 010CKWlSe

opposite direction
In the first of above examples, you can see that the phases ofp-orbitals in the starting
dienes arc different. You may also note that when thep-orbitals are out of phase before
rotation, conrotatory motion can bring them into phase for symmetry allowed overlap; and
when the y-orbitals are in phase before rotation (second example) disrotatory motion is
required. In other words, direction of rotation for symmetry allowed overlap depends on
the phases ofp-orbitals just prior to cyclisation. The phases ofp-orbitals of the diene just
prior Lo the reaction, in turn, depend on whether the molecule is in the ground state or in
the excited state. Let us consider both these cases.

When 1,9butadiene is heated, reaction takes place from the ground state. The electrons
that are used for sigma bond formation are in the HOMO, sc,. If you refer to Fig. 12.3, you
can see that the pertinentp-orbitals in this HOMO are out of phase with each other. So for
the sigma bond to form, rotation must be conrotatory. Disrotatory motion would not bring
lobes ofp-orbitals in phase for overlap.

Photo induced cyclisation takes place in the excited state. Here HOMO is n,*, in which
phases ofp-orbitals arc in phase. Therefore, the rotation of C--C sigma bonds has to be
disrotatory for a symmetry allowed reaction to take place.
 dirrotatory
bonding

=;
photo eymmetry-allowed
(in phase),

Stemhemistry of a 4n cyclisatlon

We have said above that the stereochemistq of the product in electrocyclisation dtpcnds
whether the reaction is thermally or photo induced.
OII

Let us see why. In order to study the stereochemistry of electrocyclisation of 4n systems

we will take a substituted 19-butadiene. If (2E,4Z)- hexadiene is cyclised cis-dimethyl
cyclobutene results from heating and the t r m isomer from a photochemical reaction.

As you can deduce from the discussion above, in thermal cyclisation conrotatory motion is
required for bond formation. So both methyl groups rotate in the same direction. As a
result they are on the same side of the ring or cis in the product.

therni:~l
conrotatory
7

oie
In photochemical cyclisation, on the other hand, disrotatory motion would be required for
bond formation. The two methyl groups rotate in opposite directions, one rotates up, the
other down; with the result that they are trans in the product.

I
n
3

12.5.2 Cyclisation of (4n+2)Systems

In Claisen rearrangement, the ally1 group migrates to the ortho position. However, if both rcrlcycllc k t b m
ortho positions are filled, para migration takes place, but never meta. There is no reaction
when both ortho and thepara positions are fiflled. Further, experiments with compounds
labelled with 14Chave shown that ortho migration is always accompanied by an allylic
shift where a s inpura migration there is never an allylic shift.

12.6.1 Classification of Sigmatropic Rearrangements

The method of classification of sigmatropic rearrangements differs from cycloadditions
and electrocyclic reactions. Whereas in the latter two types of reactions, classification is
based on the numberof electrons involved in the cyclic transition state, the sigmatropic
rearrangements are classified by a double numbering system that refers to the relative
position of the atoms involved in the migration. This is best explained by taking a few

CH2-CH=CH,
[1 2 31
numbering of the
alkenyl chain

As you can see both the akenyl chain and the migrating group are numbered starting at the
position of their original attachment. This may not be a carbon atom. Also these numbers
are not related to nombnclature numbers. In the above example atom 1of the migrating
group ends u p on atom 3 of the alkenyl chain, so this rearrangement is classified as [1,3]
sigmatropic rearrangement. Examples of [1,5] and [1,7] sigmatropic rearrangements are
given below. In both cases the migrating group is H.

[1,3] sigmatropic rearrangements are relatively rare, while [1,5] sigmatropic

rearrangements are fairly common. First atom of the migrating group may not always
become bonded to the alkenyl chain. In the example of Cope rearrangement given above,
atom 3 of the migrating group becomes bonded to atom 3 of the alkenyl chain. So this is
an example of [3.3] sigmatropic rearrangement.
migrating group
r------7--1
1 2

atom 3 of the
alkenyl chain 2 alkenyl chain

12.6.2 Mechanism of Sigmatropic Rearrangements

We can use frontier orbital method for analysing the mechanism of sigmatropic
rearrangements also. For the purpose of analysing the orbitals, it is assumed that the sigma
bond connecting the migrating group to its original position undergoes homolytic cleavage
to yield two radicals. You must bear in mind that this is not how the reaction takes place.
The reaction is concerted. The assumption is made to allow an easy analysis of the
molecular orbitals.

Let us first take the case of a [1,3] sigmatropic rearrangement. The products of the
hypothetical cleavage are a hydrogen atom and an allyl radical which contains three pi
'
elmrons and so three a molecular orbitals.
 H hypothetical *
I
CH2-CH=CH2 A dH2 - C H = C H ~
homolytic cleavage
allyl radical

nz 8-1 - HOMO

There are twomodes in which H can shift. In onecase the migrating grbup remains on the same
side of the alkenyl chain, such a migrating is called suprabcial. In the other the migrating
group migrates t o the opposite face of the orbital system, this is known a s
antarafacial.

If you examine the HOMO of the allyl radical in a [1,3] sigmatropic shift, you can see that
suprafacial migration is symmetry forbidden though it may be geometrically feasible.

I s orbital of H symmetry forbidden

(phase incorrect
for overlap)

HOMO transition state I

suprafacial shift

Let us see what happens in the case of antarafacial shift. You can see that this is symmetry
allowed but geometrically unfavourable. This leads to the conclusion that [1,3]
sigmatropic rearrangements should not occur readily. As mentioned above, it has been
found in practice that they are rare.
0 rsymrnetry
but geometrically
allowed
difficult

-
transition state I
a ntarafacial shift

By contrast [1,5] sigmatropic shifts are quite common. If we assume a homolytic bond
cleavage for the purpose of analysis, we have to consider r molecular orbitals of
pentadienyl radical which has five x electrons and hence five molecular orbitals shown in
Fig 12.5.

hypothetical
6~ 2-CH=CH---CH=CH2
 Which of the following sigmatropic rearmgements would proceed readily and which .
slowly? Explain.
H

12.7 SUMMARY
In this unit we have discussed pericyclic reactions. These reactions are thermal or photo
induced concetted reactions with cyclic transition sates. Pericyclic reactions have been
classified into.

I
Cycloaddition reactions
Electrocyclic reactions
Sigmatropic rearrangements

In this unit we have used the frontier orbital method for analysing the mechanism of these
reactions, according to which the electrons are assumed to flow from the HOMO of one
molecule to LUMO of the other. If these orbitals are in phase, the reaction is symmetry
allowed. If the orbitals are not in phase the reaction is symmetry forbidden.

Cycloaddition reactions of 4n and (4nt2) systems have been discussed. It has been shown
by analysis of the frontier orbitals in the ground state and the excited state that
cycloadditions of 4n systems would be photo induced while those of ( 4 n i 2 ) thermally
induced.

Elwrocylic reactions of 4n and (4n+2) systems have been discussed next. Here.p-orbita1

stereochemistry of the product. Rationale for the stereochemistry of the products obtained
in thermal and photochemical reactions has been established on this basis.

Sigmatropic rearrangements are concerted intramolecular rearrangements. These occur

suprafacially or antarafacially depending on the phases of i n t e w n g orbitals in the
HOMO of the hypothetical radical system. ?he Eacility of [1,3] and [1,5] sigmatropic shifts
has been analy& in terms of orbital symmetry and geometry of the transition state.

12.8 TERMINAL QUESTIONS

1) Identify each of the following reactions as a cycloaddition, en electrocyclisation
reaction or a sinmatro~icrcarranscement.

C02c2H5
1
CH,=CH-C-CH2-CH=CH2
I .
-
heat
CH24H-CH2CH2CH=C
\
rdL(rrd 5) Predict the products in the following:

12.9 ANSWERS

2) a) 'Ihe reaction visualises n electrons flowing fmm HOMO, x, of the diem to the
LUMO %* of the dienophilc. T k e f o n , a high electron M t y in the f o m u and
a low electrdn density in the latter would favour the reaction.

b) Photoinduced (4+2) cycloaddition is aot possible in this case. Because LUMO

%of the diem is not in phase with HOMO of the dieaophilc reactRMlwould
bt symmetry forbidden.

cround rtak \ n u ~ u"z

,

rymrnetry forbidden -

3) a) 2,4Hexadiene is a 4n polyem: Therefore, $e photochemica~elcamcyclic

nadion takes place by disrotatory motion. product would be cis-3,4-dimethyl
& r t b n Inlc-dLkS 8 4
MolrcmLr b u I n . ~ . U ~ ~

4) a) [4n] thermal reaction would involve conrotatory motlon.

b) [4n+2] photochemical reaction would involve conrotatory motion.
c) [4n]photochemical reaction would involve disrotatory motion.
d) [4n+2] thermal raection would involve disrotatory motion.

Further Readings

1) Orgrinic Ctterrtistry, 6th edition; by R .T. Morrison and R.N. Boyd; Prent icc-I Iall of
India Pvt. Ltd.

2) A Text Book of Organic Cherriistry; by B.S. Bahal and Arun Bahal; S. Chand &
Company Ltd.

3) Organic Cherrtistry, Vo1.I a!id 11; by S.M. Mukherji. S.P. Singh and R.P. Kapoor;
Wiley Eastern Ltd.

4) Tar Book of Organic Cherr~istrv,24th edition; by P.L. Soni and H.M. Chawla.
Sultan Chand & Sons.

5) Text Book of Organic Chetnistry, 2nd edition; by Llyod N. Ferguson; Affiliated_Gst

West Press Pvt. Ltd.

6) 2nd edition. by'curdeep L*.

Reaction Mechanisrrt and Reagent in Organic C/~ernistry,
Chatwal; Himalaya Publishing House.

7) Reaction Mechanisrrt in Organic Cherwhry, by S.M. Mukharji. S.P. Singh. The

Macmillan Company of India Limited.

8) Organic Chetriistry, by Pine, Hendickson, Cram. Hanmond, M c Craw-Hill

Kogakusha, Ltd. (Fourth Edition).