Pericyclic Reactions

Pericyclic reactions: Bonding changes occur through reorganization of electron pairs

within a closed loop of interacting orbitals

In order for a reaction to be pericyclic the bonding changes must be concerted,

therefore bond formation and bond cleavage occur simultaneously

If stepwise then the reaction is not pericyclic

The extent of bond formation or breakage need not be equivalent at a given point along the
reaction coordinate only that the process are both occurring simultaneously

Concerted Synchronous

What importance does knowledge of pericyclic reactions impart?

Allows prediction about whether a reaction will proceed

and also allows prediction about stereochemical control

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 Pericyclic Reactions

All pericyclic reactions have a transition state with a continuous loop of electrons in a cycle

The symmetry characteristics of the orbitals in the cycle thus determine the selection rules

Chemists R.B. Woodward and Roald Hoffmann developed rules

to predict when pericyclic reactions can occur with low energy barriers (allowed reactions)

or when they have high energy barriers (forbidden reactions)

* Called Woodward-Hoffmann rules

There are four types of reactions that are considered pericyclic:

Electrocyclic

(reactions were the first type the Woodward-Hoffmann rules were developed to explain)

Cycloadditions

(including cheletropic cycloadditions where one reactant is through a single atom)

Sigmatropic

Group Transfer

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 Pericyclic Reactions

Examples of each type of reaction:

Electrocyclic

Cyclic ring either

opens up or closes

Cycloaddition

NO2 NO2
Two compounds

react to form a ring

Sigmatropic

Bond(s) migrate over a
conjugated system

Group Transfer

H H
Transfer atoms from

one group to another

H H

All pericyclic reactions will have a defined stereochemistry depending upon

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number of electrons involved in the process

 Electrocyclic Reactions

We will begin to look at how to predict pericyclic reactions

by considering the ring closure in an electrocyclic reaction

When this E,E-2,4-hexadiene ring closes in an electrocyclic reaction,

potentially two different stereoisomers are obtained

What intrigued Woodward, however, is that only one of these stereoisomers is obtained

when the reaction is run experimentally

(and there is always only one product whenever any butadiene system ring closes)

If only one is obtained, how to predict which is favored instead of needing to run the
experiment for every new compound?

Today it seems more obvious due to the better understanding of orbital interactions in
reactions, but the approach is to always consider that the reaction must be occurring through
a molecular orbital, so if we can write the HOMO for the compound this must dictate how
the reaction proceeds
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 Electrocyclic Reactions

We have already learned how to draw a simple Hckel HOMO for butadiene

HOMO of butadiene

In the electrocyclic ring closure, the two terminal atoms react to form the new sigma bond

New bond

In order to form a bond, only orbitals of like sign can interact, therefore the symmetry of the
butadiene HOMO will dictate how the terminal atoms must move to form a bond

In order to form a bond, If orbitals move in same

the two orbitals must spin direction it is called
in the same direction
conrotatory (CON),

(both clockwise as shown)
if different directions then
disrotatory (DIS)
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 Electrocyclic Reactions

Thus a butadiene system will close in a CONROTATORY motion

An unsubstituted butadiene will generate the same cyclobutene upon ring closure

whether it undergoes a CON or DIS ring closure,

but a substituted butadiene yields different stereoisomers

FAVORED

Which is favored?

Would just need to perform a CON ring closure to determine preferred product

In the E,E-2,4-hexadiene A CON motion thus places the

compound,
H3C H3 C
CH 3 CH3 methyl groups on opposite sides
the methyl groups are pointing of the ring, therefore the trans
away from each other
product is favored

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 Electrocyclic Reactions

Any size conjugated system could form a ring through an electrocyclic reaction, a pericyclic
reaction needs an orbital on each atom of the ring interacting but size is not limited

Consider hexatriene

Would once again need to consider the HOMO for the hexatriene

(which was already determined with Hckel)

Once again the terminal

atoms combine to form
the new bond

With hexatriene,

a CON rotation gives the
Compounds can be categorized by the number of
wrong bonding scheme,

electrons in system on the preferred electrocyclic rotation

need a DIS rotation instead

4n systems CONROTATORY

4n+2 systems DISROTATORY

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 Electrocyclic Reactions

By the principle of microscopic reversibility, the ring opening reactions must proceed
through the same symmetry motions as the ring closing

Therefore in ring opening, a 4n system opens through a CON motion

while a 4n+2 system opens through a DIS motion

(methyl groups pointed in

same direction at both
double bonds)

Therefore consider a CON CH3 CH3 When this compound does a ring
motion for this cyclobutene opening through a CON motion,
ring opening with methyl CH3 CH3
the methyl groups in product
groups starting on same side
point in the same direction

Product yields are due to

symmetry of ring opening,
not stability of product!

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99.9%
0.005%

 Electrocyclic Reactions

With a CON ring opening with cyclobutene, the ring could open in two different ways

(both terminal atoms rotating clockwise or both terminal atoms rotating counterclockwise)

A C
B C A D
B D A D B C
Both rotate
Both rotate

clockwise
counterclockwise

Which product will be favored?

Orbital symmetry does not distinguish between these two structures, they both are possible

When there is a difference in sterics, however, one product can be preferred

H3 C H

H3 C
H H CH3
favored

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 Electrocyclic Reactions

Electrocyclic reactions can occur in ring opening reactions involving loss of a leaving group

OCH3
Cl CH3OH

The ring can aid in the As cyclopropane ring

leaving group departing
opens up, an allyl cation
is formed

Cl Cl
There are 2 electrons
involved in this process,
therefore ring opening is Back lobe of
disrotatory
C-Cl bond

The C-C bond anti to Rotate view so looking
leaving group, aids in at the bond breaking
leaving group departing
(and C-Cl bond is
behind in view)

The bond breaks only in the disrotatory motion that moves electrons towards

the back lobe of the C-Cl bond that is breaking
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 Electrocyclic Reactions

Will not have bond break in other possible disrotatory motion

because this motion would not aid in leaving group departing

Cl Cl
Also disrotatory, but
when electrons move
Back lobe of this way do not break
C-Cl bond
C-Cl bond

Knowing this motion, predict which of the following two isomers will react faster

krel

Cl

Cl

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 Electrocyclic Reactions

Cyclopropanes can open up in an electrocyclic reaction to aid in leaving groups at other sites,
consider this bicyclic compound

Disrotatory
OCH3
(still 2 es)
CH3OH

TsO Rotate towards

back lobe

Can thus make predictions about relative rates for isomers of this structure

krel

H
H

TsO

TsO H
H

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 Electrocyclic Reactions

Ring constraints can impact rates of normal electrocyclic ring opening reactions

Consider a cyclobutene ring opening when included in a bicyclic compound

4 es, therefore CON

H
H 200C

Would generate a trans double

bond, but ring is 10 carbons,
so Bredts rule is not violated

420C

H
H
Ring is 3 carbons shorter
Observed product is cis-cis
1,3-cycloheptadiene

Obtain forbidden pathway due to the allowed electrocyclic ring opening

would violate Bredts rule (by placing trans alkene in 7 membered ring),

thus reaction occurs at much higher temperature
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 Electrocyclic Reactions

Photochemically an electron is promoted into a higher energy molecular orbital

When considering a butadiene system, this means the symmetry of the HOMO changes

A
A

S
S

h

A
A

S
S

The HOMO is antisymmetric (A) in Upon photolysis, HOMO changes

ground state, therefore need CON
to symmetric, thus need DIS
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 Electrocyclic Reactions

Upon photolysis, therefore, the motion changes compared to the thermal process

For an electrocyclic reaction

# of electrons
Thermal ()
Photochemical (h)

4n
CON
DIS

4n+2
DIS
CON

Allows reactions that to occur that would be impossible under opposite conditions

H
h


H H
H DIS
CON

This compound can form Highly strained,

readily under photolysis
does not form

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 Cycloaddition Reactions

We have already briefly discussed cycloaddition reactions when looking at a Diels-Alder

reaction in the discussion on molecular orbital theory

A similar orbital consideration needs to be undertaken by considering the HOMO

of one reactant interacting with the LUMO of the second

(in a cycloaddition there are two molecules reacting, unlike an electrocyclic where a single
compound either forms a ring or opens a ring)

Typically the butadiene component reacts through the HOMO

and the ethylene reacts through the LUMO

LUMO

of ethylene

HOMO

of butadiene
If the symmetry was not correct,

then it would be symmetry forbidden by
Reaction is symmetry allowed
Woodward-Hoffmann rules

To increase the rate of a Diels-Alder reaction, the energy difference between the

HOMO of butadiene and the LUMO of ethylene needs to be lowered
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 Cycloaddition Reactions

Cycloadditions are further characterized by the allowed symmetry of addition

If the orbitals react on the same side of a plane, then the addition is suprafacial (S),

if the orbitals react on the opposite sides of a plane, then the addition is antarafacial (A)

Suprafacial addition
Suprafacial addition

A Diels-Alder reaction is thus formally a [4S + 2S] addition

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 Cycloaddition Reactions

When an alkene HOMO reacts with an alkene LUMO, however,

the suprafacial reaction will not be symmetry allowed

HOMO
LUMO

of alkene
of alkene

[2S + 2S]
Suprafacial addition
Suprafacial addition
forbidden

But an antarafacial addition is allowed

In a four membered ring

this orientation is hard to
reach, therefore rate of
[2S + 2A]
reaction is slow but the
allowed

stereochemistry is allowed

Antarafacial addition
Suprafacial addition

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 Additional Problems

Are the following observations allowed according to orbital symmetry conservation rules?

1)

H
H

CO2CH3
CO2CH3
CO2CH3 CO2CH3

4 electron electrocyclic ring opening,

under thermal conditions need to proceed with CONROTATORY ring opening

H H
R R =
CO2CH3
H H CO2CH3
H3CO2C CO2CH3

Therefore this reaction is allowed thermally

(it would, however, be forbidden photochemically)

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 Additional Problems

2)

6 electrons involved, photochemical electrocyclic reaction will be CONROTATORY

H
H
H
H

A photochemical opening will thus generate a trans double bond in the ring

(not the compound shown above) so it is forbidden by Woodward-Hoffmann rules

(it would be allowed thermally)

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 Additional Problems

3)

H
O
O
H
O O

Reaction shown is a 4 electron electrocyclic ring closing reaction,

therefore under thermal conditions this should be a CONROTATORY ring closure

H H
O O

O H O

In a conrotatory ring closure, the two hydrogens would move to opposite sides of the

bicyclic ring junction, not the compound shown so thermally this is a forbidden process

(it is allowed photochemically)

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