Percyclic reactions

Introduction
A pericyclic reaction represent an important class of concerted
(single step) processes involving -systems is one in which bonds
are made or broken in a concerted cyclic transition state. A
concerted reaction is one which involves no intermediates during
the course of the reaction (left). A stepwise and therefore nonconcerted and non-pericyclic reaction is shown with a discrete
intermediate (right).

Understanding
pericyclic
reactions
therefore
understanding the transition states that control them.

involves

:Properties of pericyclic reactions

1.There is no nucleophilic or electrophilic component. This means
that in the arrow pushing sense, there is no beginning and no
ending for the arrows, and the arrow pushing can occur in
either a clockwise or anti-clockwise direction.
2.Normally, no catalyst is need to promote the reactions.
However, many transition metal complexes can catalyse
pericyclic reactions by virtue of d-orbital participation. Lewis
acids also catalyse many forms of pericyclic reactions, either
directly, or by changing the mechanism of the the reaction so
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that it becomes a stepwise process and hence no longer a true

pericyclic reaction.
3.Pericyclic reactions normally show a very high stereospecificity.
4.Pericyclic reactions can be frequently promoted by light
(denoted h in the text) as well as heat (denoted in the text).
Normally, the stereochemistry under the two sets of conditions
is different, and it was (originally) thought invariably opposite.
5.Pericyclic reactions can occur in the gas phase with no solvent.
There is a relatively small solvent effect on the rate of reaction
(unless the reactants themselves happen to be charged, ie
carbonium or carbanions). Quite recently, the use of water to
accelerate pericyclic reactions (by perhaps a factor of 10 to
100) has been much investigated, but the acceleration is
largely due to the formation of hydrogen bonds specific to the
transition state.
6.It has very recently been shown that it is
to influence pericyclic
outcomes
using
quite
mechanical stress (Mechanochemistry)

possible
literally

7.The reactions can be accelerated by the use of pressure for

those involving a substantial decrease in volume. Catalysts
("molecular
containers")
also
exist
which
provide
suitable "cavities" for promoting pericyclic reactions such as
cycloadditions.
8.Unlike nucleophilic/electrophilic reactions, pericyclic reactions
are unusual in that surprisingly few enzymes which catalyse
them are known. Artificial catalytic antibodies ('abzymes') can
be created which can perform this feat, "Diels-Alderase" may
do this for cycloadditions and Chorismate mutase does do this
for
the
Claisen
rearrangement,
and
they
act via points 5 and 7 above.

Notes:
Pericyclic reactivity can be understood in terms of frontier molecular orbital
(FMO) theory and the outcome of reactions can be predicted using
the Woodward-Hoffmann rules.
Pericyclic reactions are popular with synthetic chemists because the
reagents and conditions are mild and the reactions are usually very
"clean"... unlike so many organic chemical reactions that result in the
formation of large quantities of brown-black, smelly by-product of unknown
composition...

Suprafacial: If a component undergoes addition (forms bond) on the same

face, it is called a suprafacial component .

Antarafacial: If a component undergoes addition on opposite faces, it is

called an antarafacial component.

In
a conrotatory
mode
of
an electrocyclic
reaction the substituents located at the termini of a conjugated double
bond system move in the same (clockwise or counter clockwise) direction
during ring opening or ring closure.In a disrotatory mode, they move in
opposite directions.
Correlation

diagram: A diagram which shows the relative energies of orbitals,

configurations, valence bond structures, or states of reactants and

products of a reaction, as a function of the molecular geometry, or another
suitable parameter. An example involves the interpolation between the
energies obtained for the united atoms and the values for the separated
atom.
Conservation
of
orbital
symmetry:
IUPAC
definition: The
orbital
symmetry control of concerted reactions; this requires transformation of
the molecular orbitals of reactants into those of products to proceed
continuously by following a reaction path along which the symmetry of
these orbitals remains unchanged. Reactions which adhere to this
requirement are classified as symmetry-allowed reactions, and those which
do not as symmetry-forbidden reactions.

The four principle classes of pericyclic reactions are termed:

.Cycloaddition , Electrocyclic , Sigmatropic reactions

Electrocyclic Reactions
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An electrocyclic reaction is a reversible reaction that can involve ring closure

or ring opening. An electrocyclic ring closure is an intramolecular reaction
that forms a cyclic product containing one more bond and one fewer " bond
.than the reactant

The mechanism is not particularly surprising, but the stereochemistry

changes depending on whether heat or irradiation (typically UV-light) is used
.to promote the reaction. e.g

Whether the reactant or product predominates at equilibrium depends on the

ring size of the cyclic compound. Generally, a six-membered ring is favored
over an acyclic triene at equilibrium.
In contrast, an acyclic diene is favored over a strained four-membered ring.
An electrocyclic ring-opening reaction is a reaction in which a bond of a
cyclic reactant is cleaved to form a conjugated product with one more " bond.

Electrocyclic reactions are completely stereospecific . For example,

ring closure of (2E,4Z,6E)-2,4,6-octatriene yields a single product with cis
methyl groups on the ring. Ring opening of cis-3,4-dimethylcyclobutene
forms a single conjugated diene with one Z alkene and one E alkene.

An electrocyclic reaction occurs only when like phases of orbitals can

overlap to form a bond. Such a reaction is symmetry allowed.
An electrocyclic reaction cannot occur between orbitals of opposite phase.
Such a reaction is symmetry forbidden.
To form a bond, the p orbitals on the terminal carbons must rotate so that like
phases can interact to form the new bond. Two modes of rotation are
possible.
When like phases of the p orbitals are on the same side of the molecule,
the two orbitals must rotate in opposite directionsone clockwise and one
counterclockwise.
Rotation in opposite directions is said to be disrotatory.

 When like phases of the p orbitals are on opposite sides of the molecule,
the two orbitals must rotate in the same directionboth clockwise or both
counterclockwise.
Rotation in the same direction is said to be conrotatory .

Thermal Electrocyclic Reactions

.Draw the product of each thermal electrocyclic ring closure

Solution

Count the number of " bonds in the conjugated polyene to determine the
mode of ring closure in a thermal electrocyclic reaction.
A conjugated polyene with an odd number of " bonds undergoes disrotatory
cyclization.
A conjugated polyene with an even number of " bonds undergoes
conrotatory cyclization.
a. (2E,4Z,6Z)-2,4,6-Octatriene contains three " bonds. The HOMO of a
conjugated polyene with an odd number of " bonds has like phases of the
outermost p orbitals on the same side of the molecule, and this results in
disrotatory cyclization.

b. Diene B contains two " bonds. The HOMO of a conjugated polyene with an
even number of " bonds has like phases of the outermost p orbitals on
opposite sides of the molecule, and this results in conrotatory cyclization.

Photochemical
Electrocyclic Reactions
In photochemical reactions, we must consider the orbitals of the HOMO of the
excited state to determine the course of the reaction. The excited state
HOMO has the opposite orientation of the outermost p orbitals compared to
the HOMO of the ground state. As a result, the method of ring closure of a
photochemical
electrocyclic reaction is opposite to that of a thermal electrocyclic reaction
for the same number of " bonds. Photochemical electrocyclic ring closure of
(2E,4Z,6E)-2,4,6-octatriene yields a cyclic product with trans methyl groups
on the ring.

Cyclization occurs in a conrotatory fashion because the excited state HOMO

of a conjugated triene has like phases of the outermost p orbitals on the
opposite sides of the molecule . In the conrotatory ring closure, one methyl
group is pushed down and one methyl group is pushed up, making them
trans in the product. This is a speci! c example of the general process
.observed for conjugated polyenes with an odd number of " bonds

Photochemical electrocyclic ring closure of (2E,4E)-2,4-hexadiene forms a

cyclobutene with cis methyl groups.

Cyclization occurs in a disrotatory fashion because the excited state HOMO of

a conjugated diene has like phases of the outermost p orbitals on the same
side of the molecule . In the disrotatory ring closure, both methyl groups are
pushed down (or up), making them cis in the product. This is a specific
example of the general process observed for conjugated polyenes with an
even number of " bonds.

WoodwardHoffmann rules for electrocyclic reactions

Cycloaddition Reactions
A concerted combination of two -electron systems to form a ring of atoms
having two new bonds and two fewer bonds is called a cycloaddition
reaction. Cycloadditions can be initiated by heat (thermal conditions) or light
(photochemical conditions). Cycloadditions are identi! ed by the number of "
electrons in the two reactants.
The DielsAlder reaction is a thermal [4 + 2] cycloaddition that occurs
between a diene with four " electrons and an alkene (dienophile) with two "
electrons.

A photochemical [2 + 2] cycloaddition occurs between two alkenes,

each with two " electrons, to form a cyclobutane. Thermal [2 + 2]
cycloadditions do not take place.

A suprafacial cycloaddition occurs when like phases of the p orbitals of both

reactants are on the same side of the " system, so that two bonding
interactions result.

An antarafacial cycloaddition occurs when one " system must twist to align
like phases of the p orbitals of the terminal carbons of the reactants.

In a cycloaddition we examine the bonding interactions of the HOMO of one

component with the LUMO of the second component.

[4 + 2] Cycloadditions

To examine the course of a [4 + 2] cycloaddition, lets arbitrarily choose the

HOMO of the diene and the LUMO of the alkene, and look at the symmetry of
the p orbitals on the terminal carbons of both components. Since two
bonding interactions result from overlap of the like phases of
both sets of p orbitals, a [4 + 2] cycloaddition occurs readily by
suprafacial reaction under thermal conditions.

Thermal cycloadditions involving an odd number of " bonds proceed by a

suprafacial pathway.
Because a DielsAlder reaction follows a concerted, suprafacial pathway, the
stereochemistry of the diene is retained in the DielsAlder product. As a
result, reaction of (2E,4E)-2,4-hexadiene with ethylene forms a cyclohexene
with cis substituents (Reaction [1]), whereas reaction of (2E,4Z)-2,4hexadiene with ethylene forms a cyclohexene with trans substituents
(Reaction [2]).

[2 + 2] Cycloadditions
In contrast to a [4 + 2] cycloaddition, a [2 + 2] cycloaddition does not occur
under thermal conditions, but does take place photochemically. This result is
explained by examining the symmetry of the HOMO and LUMO of the alkene
reactants. In a thermal [2 + 2] cycloaddition, like phases of the p orbitals on

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only one set of terminal carbons can overlap. For like phases to overlap on
the other terminal carbon, the molecule must twist to allow for an
antarafacial pathway. This process cannot occur to form small rings .

In a photochemical [2 + 2] cycloaddition, light energy promotes an electron

from the ground state HOMO to form the excited state HOMO. Interaction of
In Section 16.13, we learned that the stereochemistry of the
dienophile is retained in the DielsAlder product. this excited state HOMO
with the LUMO of the second alkene then allows for overlap of the like phases
of both sets of p orbitals. Two bonding interactions result and the reaction
occurs by a suprafacial pathway.

This is a speci! c example of a general cycloaddition involving an even

number of " bonds (two " bonds total, one from each alkene).
Photochemical cycloadditions involving an even number of " bonds proceed
by a suprafacial pathway.
WoodwardHoffmann rules for cycloaddition reactions

Sigmatropic Rearrangements

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Like electrocyclic reactions, sigmatropic rearrangements are unimolecular

processes. Sigmatropic reactions involve the movement of a sigma-bond with
the simultaneous rearrangement of the -system.
The [1,5] shift of hydrogen in a 1,3-pentadiene system:

Numbers in brackets refer to the two groups connected by the s bond

and designate the positions in those groups to which migration occurs

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 In a [1,5] sigmatropic rearrangement of a diene migration occurs to

position 1 of the H group (the only possibility) and to position 5 of the
pentadienyl group
In a [3,3] Claisen rearrangement migration occurs to position 3 of the
allyl group and also to position 3 of the vinylic ether
Migration of a group across the same face of the system is a
suprafacial rearrangement
Migration of a group from one face of the system to the other face is
called an antarafacial rearrangement

C2 axis of symmetryMirror symmetry

Some Examples of Sigmatropic Rearrangements

A [1,5] sigmatropic rearrangement involves three electron pairs (two
bonds and one s bond)
Orbital-symmetry rules predict a suprafacial reaction
5-methylcyclopentadiene rapidly rearranges at room temperature

13

Cope and Claisen Rearrangements are Sigmatropic

Cope rearrangement of 1,5-hexadiene
Claisen rearrangement of an allyl aryl ether

.Rearrangements; Claisen rearrang. etc [3,3]

14

C la isen rea rrangem en t

O

A lly l-v ni y le th e r o r
A lly la ry le th e r

-bond to
be b roken

1 2
3
O

1 2
3
O

15

-bond to
be fo m
r ed

tau t
H

HO