this

The
4. 5.
electronic
Woodward
There
participating
PERICYCLIC
To
ternm The
phenomenon
are
initiate
and
pericyclic
reaction
four
atoms
I. Concerted,acan
reorganisation
i.e. reactant bonds
Hoffiman)
REACTIONS are broken and
product bonds are formed
simultaneously throughkinds
occurs
become
be
a
pericyclic single transition state.
II. Involve electron reactions
shift
of
for
in a cyclic manner.
via
Pericyclic reactions have proved
no
moreintermediates but have cyclic conjugated transition
occurs
states. those
,

pericyclic
the
as
reaction,
in
(pericyclic
the
ordered
(a) Electrocyclicreactions, (b)formation
reactions
Cycloaddition
cycnc reactions, (c) Sigmatropic reactions,
and (d) Cheletropic reactions. cycIiC
reactions
thermal
means
than
of
array
Salient Features of Pericyclic Reactions whichaas
orthe
transition
1. Pericylcic reactions do not take place by ionic
or or radical
carbene
"around
have
single
or
intermediate,
1.e., reactive intermediates are not formed. follows.
reactants
the
2. Pericyclic reactions are insensitive
state
photochemical
Although
to
the
cyclic catalysts.
partAeipating
some
exceptions are
there, e.g. some cycloaddition reactions are influenced by acid catalyst and also some
in
Sigmatropic rearrangements are influenced by catalysts. following
circle")
possesses
the
transition in the transition
3. Solvent effect is negligible as there is not much charge separation
energy
atomie
state, which could be stabilised by solvent. is
transition
is
characteristics.
negative
state
suggested
centres.
in
required.
state
entran
Dy
an
which
the
opy

of activation.
 6. Pericvclic reactions involve the formation or cleavage of G bonds and consumption
or tormation ofT bonds, so at least onc ot the
reactants or products is an unsaturated
molecule.
7. The reversible and the
reactions are
cquilibrium depends on the thermodynamic
stability of reactants and products.

(More stable)

(More stable)
8. Pericvclic
reactions occur with a high degree of
selectivity. The stereoselectivity
depends on whether the reaction is thermally or photochemically induced.

Me
Me Me
h

Me
(cis-) (100%) Me
Me
(trans-) (100%)
9. The stereochenmical course depends on the number of electrons involved in the
process.

Me
Me hv/6e Me
A/6e
Ai Me
Me Me
truns-
cis
Me
Me A/te Me
hv/4e

Me Me
cis- Me
lrans
9.9. Cycloaddition reactions:
Cycloaddition reactions are reactions in which two molecules (same or different)
those
react to form ring compounds at the expense of double (or triple) bond in
each of the reacting
of t
partners. Cycloadditions are classified, first by the number
,
-electrons involved. The first example is a (4r+2) cycloaddition
I-O and the second example is (2n+2) cycloaddition. The most
important (4r+2) Cycloaddition reaction is "Diels-Alder
(4+27) Cyclohexen
Buta-1,3-diene +Ethene reaction"
Cycloaddition reactions are also classified the fact whether
on
the new o-bonds are formed on the same face of each reacting
molecule (superficial), or on opposite faces (antarafacial).
(27+ 2) Cyclobutane
Before discussing the stereochemical course of the cycloaddition like Diels-Alder reaction,
the terminology like superficial and antarafacial ways of bond formation are discussed in
short.
Antarafacial and Suprafacial Modes of Cycloadditions:
The terms suprafacial(s) and antarafacial (a) were introduced by Woodward and
Hoffmann to denote the stereochemistry of a reaction with reference faces of a system of
Tt-electrons or orbitals.
Suprafacial implies a process, which involves only one face of the system and antarafacial,
implies that both faces of the system are involved in the reaction.

8uprafacial way of
bond formation

Fig. 8, 289

antarafacial way of
bond formation

Fig. 9.300

Cycloadditions involving two different n-electron systems have four possible

combinations.
can possible
 Fig. 9. 31
i) supra-supra ii) supra-antara ii) antara-supra iv) antara-antara
It should be noted that-
i) supra-supra interactions lead to retention of configurations at the reacting centre in
question.

indistinguishable when
11)The supra-antara and antara-supra modes of interaction are

the two reacting systems are identical.

retention-inversion and
111) In supra-antara and antara-supra modes of interaction,
inversion-retention of configurations occurs respectively at the reacting centres.
at both the
iv) In antara-antara interactions, inversions of configuration take place
reacting centres.
the nature of
v) There are possible supra-supra combinations depending on
two
exo-addition and endo-addition.
interacting p-electron systems. These are termed as
reaction
Exo-and Endo-additions have been illustrated in case of Diels Alder cycloaddition
molecule or fragment and 'n' in the
A cycloaddition reaction involving m'-electrons in one
The subscripts x' and y' are either 's' or a
other is shown as mx+nyl-cycloaddition.
or antarafacial(a).
depending on whether attachment to that molecule is suprafacial(s)
and these symbols are
involved in bond formation may be o, and (nonbonding)
w
Electrons
often used as preliminary subscripts.
is (rTg+Tg)-cycloaddition. Dimerisation of
For example, Diels-Alder type cycloaddition
ethylene is (2.+T2)-cycloaddition.
forbidden reactions:
9.9.1. Symmetry allowed and symmetry reaction when HOMO and LUMO overlap in the
to a pericyclic
In case of FMO approach allowed reaction but
interaction then it is called symmetry
same phase leading to bonding then that is
HOMO-LUMO overlap is not a bonding interaction, i.e., antibonding,
when allowed and symmetry
forbidden reactions. Here the terms symmetry
known as symmetry ot these terms mentioned in case of correlation
related to the sense
forbidden are in no way
diagram.
HOMO
HOMO

LUMO LUMO

symmetry forbidden interaction

symmetry allowed interaction
(bonding )
antibonding) Fig. 9. 32
 The dashed lines identify bonding overlap, which can develop as the reaction proceeds. It
must be noted that symmetry forbidden reaction can also occur but not in a concerted
manner.

9.10. Frontier Molecular Orbital (FMO) approach of Cycloaddition Reactions:

For
a cycloaddition between two components to occur, there must be bonding overlap
between the p-orbitals at the terminal carbons at each n-electron system. The feasibility of a
Concerted 18 determined by whether overlap between the HOMO,or one
process can occur

componentand the LUMO of the other. If we take a case of (4n+2) electrocyclic addition, the
HOMO-LUMO combinations can be shown as follows.

LUMO of diene (W)

HOMO of diene (y2

LUMO of ene (y)

HOMO ofene (y)

Fig. 9. 33 Fig. 9. 34

Thus, in the electrocyclic (47+27] addition between a diene and a monoene, both the
above situations are bonding and is symmetry allowed in supra-supra mode of interactions.
The situation is different in case of (2n+2) cycloaddition reaction. If we put HOMO of
one monoene against LUMO of the other, they cannot give us bonding overlap. Therefore,
( t s ) cycloaddition is not symmetry allowed which is suprafacial on both components.
Thus thermal cycloaddition of (2n+2) type is forbidden.

LUMO (y"
antibonding bonding
interaction interaction
HOMO (v,
Fig. 9.355
It should be noted that the cycloadditions of (27+27) type are symmetry allowed under
thermal condition if supra-antara interactions can occur but that is geometrically difficult

This is shown in the following diagram (Fig. 9.36).

-88 HOMO of ene

LUMO ofene

Bonding overlap of thermal 2s + r2a cycloaddition

Fig. 9. 36

However, photochemical cycloaddition of two monoenes would be symmetry allowed. as nhoto-

energy (hv) will promote an electron of HOMO(bonding)to HOMO (antibonding). Under this
ndition HOMO of the exited state has the proper orbital symmetry to interact in a bonding
other reacting monoene.
way with
the LUMO (7*) of the
 LUMO (V)
hv

HOMO (V) HOMO (excited) (v,) HOMO (excited)(y,)

Fig. 9. 37 (bonding overlap
suprafacial on both components)
Fig. 9.388

Instead of supra-supra, antara-antara interaction also gives photochemical dimerisation

cycloaddition). Indeed, many examples of photochemical ?, + n2, cyeloadditions are known
and this type of cycloadditions are widely used
for making cyclobutanes.
Ph Me
Ph H Me Me
hv
-Me

-Me
H Ph Me Me Ph Me

(E)-1,2-diphenylethene 2,3-Dimethylbut-2-ene cyelobutane derivative

(E)-Stilbene
Fig. 9.39
Since it is a case of suprafacial-suprafacial mode of interaction, stereochemistry of the
reactants is retained in the product.
9.10.1. Selection Rules for Cycloaddition Reactions:
Number of T electrons Mode of activation Allowed stereochemistry
involved
4n Thermal - Supra-Antara or Antara-Supra
4n Photochemical Supra-Supra or Antara-Antara
4n+2 Thermal Supra-Supra or Antara-Antara
4n+2 | Photochemical Antara-Supra
n = 1,2,3,4 . etc.

9.11. Diels-Alder reaction:

Diels-Alder reaction is the most widely studied [4+2n]-cycloaddition reaction and,
therefore, needs some special attention.
Diels-Alder reaction is a reversible cyeloaddition, that is, diene with 4r-electrons reacts
with a 2t-electron dienophile Ir*sttg, suprafacially on each component, to form a six-
membered cyclic system, Since it is (4n+21t)-electron reaction, it is thermally feasible in
in Diels-Alder cycloaddition reaction, retention of
supra-supra allowed stereochemistry. Thus,
stereochemistry has been observed in both the diene and dienophile parts.

Me
H 37C
2 hours
H
Me
(2E,4E)-Hexa-2,4-diene (s-cis) Maleic anhydride Diels-Alder adduct
Fig. 9. 40
 conformation. If
must react in its s-cis
It is to be noted that diene part of the components
8-cis conformation, Diels-Alder cycloaddition does not
steric factors prevent a diene to assume
Diels-Alder cyclisation.
Occur. For example, the following dienes do not undergo
CH
H
Me
Me C H
Me : Me,C H

CH
H
(22,42)-2,4-Hexadiene 2,3-Ditertiarybutylbuta 2-Cyclohexenylidene Bicyclo [44-0]
(a) -1,3-diene (c) deca-1,9-diene
(b) (d)
Fig. 9. 41
In the (a) and (b), s-cis forms are unfavourable conformations due to strong steric
interactions and, therefore, s-trans forms are more stable conformations but s-trans forms
cannot give Diels-Alder cyclisation because geometry does not permit orbital overlap.
In the cases of (c) and (d), conjugated dienes are locked in s-trans forms and they cannot
assume s-cis form which is a must for Diels-Alder reaction to occur.
The compound (e) is a diyne and it has a linear and planar structure. Unlike conjugated
diene, (e) cannot assume bent s-cis conformation due to excessive strain involved and that is
why conjugated diynes do not undergo Diels-Alder cyclisation.
Orbital overlaps between diene (4T-electron system) part and dienophile (2-electron
system) part in Diels-Alder cyclisation can be shown as follows.

HOMO of diene -LEMO of diene

(
LUMO of dienophile

Fig. 9.42
(y2 &8 HOMO of dienophile

Fig. 9. 48
()
In both the cases we get supra-supra bonding overlap and, therefore, this cycloaddition is
thermally allowed. Buta-1,3-diyne
(e)