5 Pericyclic Reactions

Prof. S.
Sankararaman
Engineering Chemistry III
Pericyclic Reactions
Definition:
1. Concerted reaction that proceed via a cyclic transition state
2. No distinct intermediates in the reaction
3. Bond forming and bond breaking steps are simultaneous but not necessarily
synchronous
Classification:
1. Electrocyclic ring closing and ring opening reaction
2. Cycloaddition and Cycloreversion reaction
3. Sigmatropic Rearrangements
4. Chelotropic Reaction
5. Group transfer Reaction
Methods of Analyzing Pericyclic Reaction
1. Orbital symmetry correlation method
(Woodward, Hoffmann, Longuet-Higgins and Abrahamson)
2. The frontier orbital method
(Woodward, Hoffmann and Fukui)
3. Transition state aromaticity method
(Dewar and Zimmerman)
Woodward-Hoffmann Rules: Predicts the allowedness or otherwise of pericyclic reactions
under thermal and photochemical conditions using the above methods. Therefore a basic
understanding of molecular orbitals of conjugated polyene systems and their symmetry
properties is essential to apply the above methods.
1
Indian Institute of Technology Madras
Prof. S. Sankararaman
Constructing MO diagram of polyene systems:

1. Although there are C-C and C-H sigma bonds present in the molecule, the MOs
can be constructed independently of them. Although there may be a change in the
hybridization of carbon atoms during the course of a pericyclic reaction, the MO
levels of the sigma framework are relatively unaffected.
2. For a conjugated polyene system containing n (n = even) electrons, there will be
n/2 bonding molecular orbitals that are filled MOs and n/2 antibonding MOs that
are empty in the ground state electronic configuration of the molecule.
3. The lowest energy MO has zero nodes, the next higher one has one node and the
second higher has two nodes and so on.
The nth MO will have (n-1) nodes.
4. The nodal points are found at the most symmetric points in a MO.
In other words, no MO can be symmetric as well as antisymmetric at the same time
with respect to any existing molecular symmetry element. For example the 2 MO
of butadiene has a node at the center of the bond connecting C2 and C3. It is
incorrect to assign this node to the center of the bond connecting C1 and C2.
node
node
2
Correct
2
Incorrect
2
Formation of MOs of butadiene from MOs of ethylene
4
ethylene
butadiene
3
ethylene
MOs of ethylene Butadiene and hexatriene
antibonding
4
3
bonding
1
1
4
Frontier orbital method:

Highest occupied MO (HOMO) filled
Lowest unoccupied MO (LUMO) empty
Analysis based on the interaction of HOMO of one Component and LUMO of the other
component.
If HOMO-LUMO interaction leads to bonding then the reaction is allowed. If not it is
forbidden.
HOMO-LUMO gap is important. The closer it is the faster the reaction.
ELECTROCYCLIC REACTIONS
1. Cyclization of an acyclic conjugated polyene system
2. The terminal carbons interact to form a sigma bond
3. Cyclic transition state involving either 4n electrons or 4n+2 electrons.
(1)
(2)
Electrocyclization of butadiene (4n) and hexatriene (4n+2)
5
Modes of ring closing/ring opening reactions - Stereochemistry
H3C
CH3
conrotatory
CH3
CH3 H
H
cis
H3C
conrotatory
H
CH3H3C
CH3
H
H3C
H3C
H
E, E
6
(4)
H3C
CH3
H
H
CH3
cis
conrotatory
trans
disrotatory H
Z, Z
CH3
(3)
trans
trans
CH3
H3C
Z, E
disrotatory H
disrotatory H
H3C
cis
CH3
(5)
Frontier orbital method for electrocyclic reactions
conrotation
2 HOMO of butadiene
bonding interaction
in the TS
bonding orbital
antibonding interaction
in the TS
antibonding orbital
disrotation
2 HOMO of butadiene
disrotation
bonding interaction
in the TS
3 HOMO of hexatriene
bonding orbital
conrotation
3 HOMO of hexatriene
in the TS
7
antibonding orbital
disrotation
HOMO of excited
state butadiene
bonding interaction
in the TS
bonding orbital
conrotation
in the TS
HOMO of excited
state butadiene
antibonding orbital
conrotation
bonding orbital
HOMO of excited
state hexatriene
bonding interaction
in the TS
disrotation
antibonding orbital
HOMO of excited
state hexatriene
in the TS
8
Woodward Hoffmann rules for electrocyclic reactions
System
(no of electrons)
Mode of reaction
4n
conrotatory
allowed
forbidden
4n
disrotatory
forbidden
allowed
4n+2
conrotatory
forbidden
allowed
4n+2
disrotatory
allowed
forbidden
Allowedness of the reaction

Thermal
Photochemical
Four-membered Ring Systems:

The synthesis of cyclobutene was first reported by Willsttter. The thermal ring opening of
cyclobutene occurs readily at 150 oC to give 1,3-butadiene.
150 C
Thermal isomerization of cyclobutene to 1,3-butadiene

The stereochemistry of the ring opening has been studied systematically in detail by
Vogel and Criegee even before the theory of pericyclic reactions and WoodwardHoffmann rules were developed. The electrocyclic ring opening of 3,4-disubstitued
cyclobutenes yield products arising from the conrotatory mode of ring opening with high
stereospecificity as illusrated below.
9
Me
Me
Me
H
H
150 oC
H
Me
Me
Me
H
Me
Me
only E, Z isomer
Me
Me
Me
H
150 oC
Me
H
Me
H
H
Me
Me
only Z, Z isomer
Ph
Ph
Me
Me
Me
Me
Me
H
E, E isomer
not formed
COOMe
COOMe
Me 70 oC
Ph
Me
COOMe
Ph
Me
COOMe
Me
Stereochemistry of thermal electrocyclic ring opening of cyclobutenes.

Thermal isomerization of the highly substituted dienes shown below takes place through
the formation of the cyclobutene intermediate by a conrotatory pathway. None of the
symmetry disallowed disrotatory products were formed even after 51 days at +124 oC
which allowed the estimation of a lower limit of 7.3 kcal/mole of energy difference
between the conrotatory and disrotatory modes of reaction.
10
Stereoselective thermal isomerization of 1,3-butadiene derivatives.

CH3
Ph
Ph
Ph
CD3
Ph
Ph
Ph
Ph
Ph
Ph
Ph
CH3
Ph
Ph
CD3
Ph
Ph
CH3
Ph
CD3
CH3
CH3
or
CD3
Ph
Ph
Ph
Ph
Ph
CD3
51 days at 140 C
The photochemical ring closing of butadiene and E,E and Z,E-hexa-2,4-diene has been
studied by Srinivasan and the reaction follows the disroatory mode as predicted by the
Woodward-Hoffmann rules.
h
253 nm
Photochemical electrocyclization of 1,3-butadiene derivatives.
Benzocyclobutene is another well studied 4 electron system and the electrocyclic ring
opening gives a very reactive intermediate, namely ortho quinodimethane.
11
Thermal isomerization of benzocyclobutene to ortho quinodimethane.
Stereoselective thermal isomerization of benzocyclobutene derivatives
Ph
Ph
Ph
rt
TCNE
CH2Cl2
Ph con
meso
Ph
CN
CN
CN
Ph
quantitative
Ph
Ph
Ph
rt
H CN
H CN
TCNE
CH2Cl2
Ph con
racemic
Ph
Ph
CN
CN
CN
quantitative
Examples of thermal and photochemical electrocyclic reaction of cyclohexadienehexatriene system are abundant in the literature.] According to the Woodward-Hoffmann
rules this six electron system is predicted to undergo disrotatory cyclization under
thermal and conrotatory ring closure under photochemical conditions.
octatrienes
conform
to
the
above
predictions
and
undergo
Isomeric
stereospecific
electrocyclization as shown below.

Stereospecific electrocyclic ring closure of isomeric hexa-1,3-5-trienes.
Me
H
H
150 oC
dis
Me
Me
Me
H
o
Me 150 C
dis
H
Me
12
Me
Me
The photochemical reaction proceeds by a conrotatory ring closure / opening mode and in
general a photostationary state is reached consisting of an equilibrium mixture of both the
hexatriene and cyclohexadiene (shown below).
Stereospecific thermal ring closure of triphenylhexatrienes.
Ph
Ph
H
H
Ph
Ph
80 oC
dis
92 %
Ph
Ph
Ph
Ph
Ph
Ph
o
Ph 110 C
dis
H
110 oC
Ph
> 90 %
Ph
dis
Ph
> 90 %
Ph
Photochemical electrocyclic ring opening / closure of cyclohexdiene / hexatriene

systems
Me
H
H
dis
Me
Me
Ph
Ph
Me
Me
H
H
Me
Ph
Ph
Me
Ph
Ph
Me
Me
H
Me
Ph
Ph
13
Me
Me
CYCLOADDITION REACTIONS
1. Reaction of two components to form a cyclic compound
2. Ring forming reactions
3. Pericyclic type both components are systems
4. Intramolecular and intermolecular versions
Classification
Based on the number of electrons involved in each component
The numbers are written within a square bracket e.g. [2 + 2], [2 + 4] etc
EXAMPLES OF CYCLOADDITION REACTIONS

[2 + 2]
[4 + 2]
[4 + 4]
[4 + 6]
O
[14 + 2]
NC
CN
NC
CN
H
NC
H
CN
CNCN
14
Stereochemistry of cycloaddition reactions

Suprafacial and antarafacial approaches to a bond
suprafacial
approach
antarafacial
approach
syn addition
anti addition
It is necessary to specify with respect to each component whether the approach is

suprafacial or antarafacial
The cycloaddition of ethylene to form cyclobutane is a [2s + 2s] process. The thermal
Diels-Alder reaction is a [4s + 2s] process
Frontier Orbital Method:
HOMO-LUMO interaction for a [2s+2s] cycloaddition.
LUMO
LUMO
anti bonding
both bonding
HOMO
[2s + 2s]
[2s + 2s]
thermally forbidden
photochemically allowed
15
HOMO
[ethylene]*
HOMO-LUMO interaction for a [4s+2s] cycloaddition
LUMO
HOMO
butadiene
[butadiene]*
anti
bonding
HOMO
ethylene
LUMO
ethylene
[4s + 2s]
photochemically forbidden
HOMO
butadiene
LUMO
ethylene
[4s + 2s]
thermally allowed
Concerted [2+2] cycloaddition reactions of alkenes
1. Convenient way to form cyclobutanes

2. Reaction occurs from singlet excited -* state
3. Triplet sensitizer is required to form T1 state
4. Acyclic alkenes undergo competing cis-trans isomerization
16
5. Reaction is generally suprafacial-suprafacial additon and hence highly

stereospecific
Photochemical [2 + 2] Cycloadditions:
The concerted photochemical [2 + 2] cycloaddition reaction is suprafacial on both of
the systems. The dimerization of cis- and trans-2-butene have been reported to take
place in a highly stereospecific manner. The structure of the four possible isomers are
given in Scheme below. The original 2-butene fragment in the product is shown by thick
lines. Only two isomers namely the cis-syn-cis (syn) and the cis-anti-cis (anti) isomer are
formed when pure cis 2-butene was photolysed in the liquid state. Similarly when pure
trans-2-butene was photolysed it gave only trans-anti-trans and cis-anti-cis isomers. The
fourth isomer, namely cis-anti-trans, was formed only when a mixture of cis- and trans2-butene was photolysed. This experiment clearly points to the fact that the reaction is
highly stereospecific and suprafacial in each of the reacting partners.
Photochemical cycloaddition reactions of cis- and trans-2-butene.
h
direct
+
anti / syn = 0.8
direct
h
direct
+ the above products
Chapman has reported an efficient photochemical cross addition of trans-stilbene with

tetramethylethylene with high quantum yield ( = 1.0) and high stereospecificity. The
inverse dependence of the rate of cycloaddition with temperature provided evidence for
an exciplex formation.
17
Photochemical cross addition of trans-stilbene and tetramethylethylene
Ph
Ph
hv
Via exciplex, = 1.0
Ph
Ph
[2+2] Photocycloadditions of cyclic alkenes
H
H
h
acetone
H
H
H
H
H
H
+
H
H
sens = PhCOCH3
12 : 88
Synthesis of cage structures by photochemical cycloaddition

H
H
h
cyclohexane
62 %
H O
h
H
acetone
O
O
O
MeO
basketene
OMe
1. h
2. H+
pentaprismane
18
Diels-Alder Reaction:
Thermal cycloaddition between a cisoid conjugated diene and a dienophile, usually a
olefin or an acetylene
Six membered ring is formed
It is a concerted [4s + 2s ] addition
R1
+
CHR3
CHR4
*
*
*
R2
Diels-Alder Diene
s-transoid
s-cisoid
conjugated transoid dienes
>>
>
transoid
>
Order of reactivity of cyclic conjugated dienes
19
cisoid
Dienophiles:
CN
CN
CN
NC
CN
COOCH3
NC
CN
NC
CN
COOCH3
COCH3
O
O
COOCH3
O
N
N
N-Ph
The cis rule :
COOEt
R
HH O O
H
COOEt
COOEt
O
R
COOEt
HH O
R = Me, Ph
COOEt
R
HH O O
O
RH
COOEt
COOEt
R
R = Me, Ph
20
COOEt
H
Me
Me H
H
COOH
COOH
H
COOH
Me
Me H
Me H
COOH
Me
COOH
H
COOH
H
COOH
Me HOOC
COOH
Me H
Alders endo rule (secondary orbital interactions):
rt
H
H
rt
H
HO
O
+
HOMO
LUMO
O
O
21
COOH
COOH
COOH
Regioselectivity in Diels-Alder reaction:
R
R'
R'
+
R'
"ortho"
R'
"meta"
R'
+
R'
"para"
"meta"
Diels-Alder reactions are highly ortho/para selective.

The regioselectivity in Diels-Alder reactions is exemplified below
R
X
R
X
X
R
ortho
meta
Me
COOMe
89
11
OAc
COOMe
100
OMe
COOMe
100
OMe
CN
100
OMe
CHO
100
X
R
para
meta
80
20
100
Me
COOMe
Me
CHO
OMe
COMe
100
OMe
CHO
100
22

5 Pericyclic Reactions

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5 Pericyclic Reactions

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Prof. S.

Engineering Chemistry III

Engineering Chemistry III

Constructing MO diagram of polyene systems:

Engineering Chemistry III

Formation of MOs of butadiene from MOs of ethylene

Engineering Chemistry III

MOs of ethylene Butadiene and hexatriene

Engineering Chemistry III

Frontier orbital method:

Electrocyclization of butadiene (4n) and hexatriene (4n+2)

Engineering Chemistry III

Modes of ring closing/ring opening reactions - Stereochemistry

Engineering Chemistry III

Frontier orbital method for electrocyclic reactions

Engineering Chemistry III

Engineering Chemistry III

Woodward Hoffmann rules for electrocyclic reactions

Allowedness of the reaction

Four-membered Ring Systems:

Thermal isomerization of cyclobutene to 1,3-butadiene

Engineering Chemistry III

Stereochemistry of thermal electrocyclic ring opening of cyclobutenes.

Engineering Chemistry III

Stereoselective thermal isomerization of 1,3-butadiene derivatives.

Photochemical electrocyclization of 1,3-butadiene derivatives.

Engineering Chemistry III

Thermal isomerization of benzocyclobutene to ortho quinodimethane.

Stereoselective thermal isomerization of benzocyclobutene derivatives

electrocyclization as shown below.

Engineering Chemistry III

Photochemical electrocyclic ring opening / closure of cyclohexdiene / hexatriene

Engineering Chemistry III

EXAMPLES OF CYCLOADDITION REACTIONS

Engineering Chemistry III

Stereochemistry of cycloaddition reactions

It is necessary to specify with respect to each component whether the approach is

Engineering Chemistry III

HOMO-LUMO interaction for a [4s+2s] cycloaddition

Concerted [2+2] cycloaddition reactions of alkenes

1. Convenient way to form cyclobutanes

Engineering Chemistry III

5. Reaction is generally suprafacial-suprafacial additon and hence highly

+ the above products

Chapman has reported an efficient photochemical cross addition of trans-stilbene with

Engineering Chemistry III

Photochemical cross addition of trans-stilbene and tetramethylethylene

Via exciplex, = 1.0

[2+2] Photocycloadditions of cyclic alkenes

Synthesis of cage structures by photochemical cycloaddition

Engineering Chemistry III

conjugated transoid dienes

Order of reactivity of cyclic conjugated dienes

Engineering Chemistry III

The cis rule :

Engineering Chemistry III

Alders endo rule (secondary orbital interactions):

Engineering Chemistry III

Regioselectivity in Diels-Alder reaction:

Diels-Alder reactions are highly ortho/para selective.

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