PERICYCLIC REACTIONS

PERICYCLIC
REACTIONS
peri =around, cyclic = circle or ring
Polar react. (nucleophiles and electrophiles)
Nu E

Radical react.
R R'

Pericyclic react. (concerted, cyclic TS#)

Electrocyclic react.
Rearrangement of polyene
Cycloadditions (i.e. Diels Alder)
Termal (react. in ground state)
Sigmatropic rearrangement or photochemical
(react of exited state)
 Involves several simultaneous bond-making breaking process
with a cyclic transition state involving delocalized electrons.

The combination of steps is called a concerted process where

intermediates are skipped
Any concerted reaction in which bonds are formed or broken in
a cyclic transitions state. (electrons move around in a circle).

Concerted reaction Multistep reaction

Transition state Transition states

Energy Energy
inter-
starting starting mediate inter-
product mediate product
material material

reaction co-ordinate reaction co-ordinate

Properties of pericyclic reactions:

(a) Little, if any, solvent effect.

(b) No nucleophiles or electrophiles involved.

(c ) Not generally catalysed by Lewis acids.

(d) Highly stereospecific.

(e) They are initiated by either heat (thermal initiation) or

light (photo initiation)
 Examples of pericyclic reactions:
1) Electrocyclisation reactions:- Linear conjugated polyene
converted into a cyclic product in one step. 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.

5
2) Cycloaddition reactions:- Two linear conjugated polyenes
converted onto a cyclic product in one step. Again, the
stereochemistry of the reaction is remarkably reproducible. e.g.
3) Sigmatropic rearrangement reactions:-These involve a
concerted migration of atoms or of groups of atoms. E.g.
migration of a s-bond. The numbering refers to the number of
atoms in the transition state on either side of where bonds are
made or broken.
 Frontier Molecular Orbitals

In order to understand the selectivity of pericyclic reactions,

we need to understand these molecular orbitals and how
they overlap.

In particular, we need to know how the Frontier Molecular

Orbitals (FMOs) interact in the starting material(s) which
lead to the cyclic transition states.

We will first revise some simple molecular orbitals of a C-H

s-bond and a C=C -bond and then extend this analysis to
highly conjugated linear polyenes and related structures
 Introduction of Frontier Molecular Orbitals

(i) Given a set of n p-orbitals you should be able to construct a

molecular orbital energy level diagram which results from
their combination.

(ii) In this diagram you should be able to identify for each MO

()nodes

()the symmetric (S) or antisymmetric (A) nature of the MO

towards a C2 axis or mirror plane

()the bonding, nonbonding or antibonding nature of it.

(iii) For a set of n molecular orbitals you should be able to identify the
frontier molecular orbitals.
the highest occupied molecular orbital (HOMO )
the lowest unoccupied molecular orbital (LUMO)

(iv) The HOMO (thermal reaction) interactions are important when

evaluating the probability of an unimolecular reaction occurring and the
stereochemical outcome see electrocyclic reactions.

The HOMO/LUMO (thermal reaction) interactions of the reacting

species are important when evaluating the probability of (i) a
bimolecular reaction occurring and the stereochemical outcome see
cycloaddition reactions, and (ii) a unimolecular reaction occurring and
the stereochemical outcome see sigmatropic reactions.

The geometry, phase relationship and energy of interacting HOMOs

and LUMOS is important for evaluating the probability of a reaction
occurring and the stereochemical outcome.
 -Bond
Two s Atomic Orbitals
Molecular Orbitals

Nodal Plane
ANTI-BONDING
MOLECULAR
ORBITAL

E
N
*
E
R
G
+ s ATOMIC ORBITAL

BONDING
MOLECULAR
ORBITAL

 -Bond
One s Atomic Orbital and One sp3 Atomic Orbital

Molecular Orbitals

ANTI-BONDING
MOLECULAR
ORBITAL
E
N *
E
R
sp3 ATOMIC ORBITAL
G
Y
+

BONDING
MOLECULAR
ORBITAL

-Bond:
Two p Atomic Orbitals Molecular Orbitals
Nodal Plane

ANTI-BONDING
MOLECULAR
ORBITAL

E *
N
E p-atomic orbitals
R +
G
Y

BONDING
MOLECULAR
ORBITAL

The linear combination of

n atomic orbitals

leads to the formation of

n molecular orbitals
A Molecular Orbital Description of
Ethane
Asymmetric
(LUMO)

(HOMO)

Symmetric
Four p atomic orbitals interact to give the four p MOs of
1,3-butadiene

(LUMO)
Asymmetric

Symmetric (LUMO)(HOMO)

(HOMO)

Asymmetric

Symmetric
 NOTE
A MO is bonding if the number of bonding interactions is
greater than the number of nodes

A MO is antibonding if the number of bonding

interactions is fewer than the number of nodes

The normal electronic state of a molecule is known as

its ground state

The ground state electron can be promoted from its

HOMO to its LUMO by absorption of light (excited state)

In a thermal reaction the reactant is in its ground state;

in a photochemical reaction, the reactant is in its excited
state
A Molecular Orbital Description of 1,3,5-hexatriene

Asymmetric

(LUMO)
Symmetric

(LUMO) (HOMO)
Asymmetric
(HOMO)
Symmetric

Asymmetric

Symmetric
The Allyl Cation, Radical and Anion 3p AOs to give 3 MOs

Cl Cl H

Polar
Solvent
B

Cl Cl BH
Allyl Cation Allyl Radical Allyl Anion
Thus, allyl systems result from the combination of 3 conjugated p-
orbitals. Therefore, this will result in 3 -molecular orbitals.

When we constructed the -molecular orbitals of ethene, each

contributing AO was the same size, i.e. the coeffecient c were
1/2 or -1/2.

When there are three or more p-atomic orbitals combining the

size of each contributing p-atomic orbital will not be equal
(but they will be symmetrical about the centre).
 LUMOs and HOMOs

LUMO = Lowest Unoccupied Molecular Orbital

HOMO = Highest Occupied Molecular Orbital

Allyl Allyl Allyl

Cation Radical Anion
(2e) (3e) (4e)

3 LUMO LUMO
2 nodes

2 1 node LUMO HOMO HOMO

1 0 nodes HOMO
 - molecular boning of Pentadiene
Pentenyl Pentenyl Pentenyl
O
cation (4e) radical (5e) anion (6e)

Pentenyl
cation (4e)
Mirror Plane C2 axis

5 5 4 nodes
4 nodes S A

4 4 3 nodes
3 nodes LUMO
A LUMO
S

3 3 2 nodes
2 nodes LUMO
LUMO S
HOMO A
HOMO

2 2 1 node
1 node HOMO A S
HOMO

1 0 nodes S A
1 0 nodes
 ELECTROCYCLIC REACTION
These are pericyclic processes that involves the cyclization of a
conjugated polyene. The electrocyclic reactions are
intramolecular reactions.

One bond is broken, the other bonds change position, a new

bond is formed, and a cyclic compound results.

Gives specific stereoisomeric outcomes related to the

stereochemistry and orbitals of the reactants
 Conservation of Orbital Symmetry Theory

In 1965 R.B. Woodward and Roald Hoffmann developed

this theory
Explains the relationship among the structure and
configuration of the reactant, the conditions (thermal or
photochemical) under which the reaction takes place, and the
configuration of the products,

States that in-phase orbitals overlap during the course of a

pericyclic reaction
An electrocyclic reaction is completely stereoselective
Only the symmetry of the HOMO is important in determining the
course of the reaction
 A symmetry-allowed pathway is one in which in-phase
orbitals overlap

If a reaction is symmetry-forbidden, it cannot take place

by a concerted pathway

The symmetry of the HOMO of the compound undergoin

ring closure controls the stereochemical outcome of an
electrocyclic reaction
 Photochemichal condition

Thermal condition
 Thermal condition
h

Photochemichal condition
Rules for Electrocyclic
Reactions
 Frontier Molecular Orbital Method
It is an easy and extremely simple approach that is based on
the interaction of the frontier orbitals, i.e., the highest occupied
molecular orbital (HOMO) and the lowest unoccupied
molecular orbital (LUMO) of the components that are involved
in a pericyclic reaction.

When two systems come close to each other, then their

unperturbed molecular orbitals start to interact and those that
are close in energy interact more strongly than other orbitals. It
is well known that interaction of two filled MOs does not lead
to the net energy stabilization of the system but it is the
interaction between one filled and other vacant MO that leads
to net energy stabilization. This explains why interaction
between HOMO and LUMO is considered in this approach
 If interaction between these two MOs is of bonding type
(overlapping of same signed wave functions) in the ground state,
then reaction is thermally allowed. However, if it is of antibonding
type (overlapping of opposite signed wave functions) then it is a
thermally forbidden reaction.

On the other hand, if interaction between HOMO & LUMO is

of bonding type in the excited state, then reaction is photochemically
allowed. However, it is a photochemically forbidden reaction when
it is of antibonding type.
 In order to apply the FMO approach in unimolecular
pericyclic reactions like electrocyclic reactions and sigmatropic
rearrangements, we have to treat a single molecule as having
separate components. In such a case, only HOMO of the
component has to be considered to predict the feasibility of the
reaction under given conditions.
2
3
Q4

Q5
Q6
Q 9
 CYCLOADDITION REACTIONS
Cycloaddition reactions are intermolecular pericyclic processes involving
the formation of a ring from two independent conjugated systems through
the formation of two new -bonds at the termini of the -systems. The
reverse process is called cycloreversion or is referred to as a retro-reaction.

Suprafacial HOMO 2

Suprafacial Sub Sub LUMO 2

(i) A cycloaddition reaction involves the formation of two bonds
between the termini of two independent -systems, resulting in
ring formation - or the reverse process.

(ii) Cycloaddition reactions are stereospecific (e.g. cis/trans isomers).

The stereospecificity being afforded by the suprafacial or
antarafacial nature of the approach of the two -units in the
transition state.

(iii) The suprafacial or antarafacial process involved in the bond

making process is controlled by the HOMO/LUMO interactions of
the two -systems in the transition state.
(vi) Cycloaddition reactions can be regioselective. The
regioselectivity cannot be predicted from the simple
treatment given to frontier molecular orbitals in this
course. However, generalisations can be made from
looking at classes of substituents (C, Z, X) which are in
conjugation with the -systems, which allow us to predict
the regioselectivity in an empirical manner.
The Questions FMO Theory Can Answer
150C
85%
10 days

0%

165C
78%
900 atm

17 hours
 Rules for Cylcoadditions -
Suprafacial Cycloadditions
The terminal lobes of the two reactants must
have the correct symmetry for bonding to
occur
Suprafacial cycloadditions take place when a
bonding interaction occurs between lobes on
the same face of one reactant and lobes on
the same face of the other reactant

58
 Rules for Cylcoadditions -
Antarafacial Cycloadditions
These take place when a bonding interaction
occurs between lobes on the same face of one
reactant and lobes on opposite faces of the
other reactant (not possible unless a large ring
is formed)

59
Frontier Orbital Analysis of a [4 + 2]
Cycloaddition Reaction
A [2 + 2] Cycloaddition Reaction
Frontier Orbital Analysis of a [4 + 2]
Cycloaddition Reaction
 Frontier MO Analysis of the
[2 + 2] Cycloaddition Reaction
Diels-Alder Cycloaddition Reaction:
6 -Electron Transition State

Suprafacial 2 HOMO
4s + 2s

Suprafacial 2 LUMO
Diels-Alder Reaction Transition State Geometry

Suprafacial

Diene HOMO 2

EWG EWG
EWG EWG EWG EWG

MESO
Dieneophile LUMO 2

Suprafacial

4s + 2s
 Suprafacial
One of two equally
likely transition states
Diene HOMO 2 See Next 2 Slides

EWG EWG EWG

EWG

EWG
EWG

EWG EWG
Dieneophile LUMO 2

Suprafacial
i.e. enantiomers

4s + 2s
Regiochemistry Issues in the Diels-Alder
Reaction

C/Z/X C/Z/X
C/Z/X C/Z/X

X X

Except

X X

C = Extending Conjugation

Z = Electron Withdrawing Group

X = Electron Donating Group

 X/Z/C X/Z/C

C/Z/X C/Z/X

X X
X X
Except

C = Extending Conjugation

Z = Electron Withdrawing Group

X = Electron Donating Group

endo - exo selectivity
O

O O O Endo O
Exo
O O
O O O O
O

HOMO - Diene HOMO - Diene

Primary interact., bond formation

Secondary interact., extra TS# stabil.

O O O LUMO - dienophile
O O O

al electron demand DA - Electron poor dienophile (Michael accept.)

Ethene etc, very low react.

Michael accept. LUMO -alkene
LUMO -alkene
Lower LUMO
EWG

HOMO - LUMO gap

EWG
HOMO-alkene

HOMO-alkene
 30.8 Sigmatropic
Rearrangements
A -bonded substituent atom or group
migrates across a p electron system from one
position to another
A bond is broken in the reactant, the p bonds
move, and a new s bond is formed in the
product

84
 Sigmatropic Rearrangements

3,3] Rearrangements; Claisen rearrang. etc.

Claisen rearrangement

Allyl-vinyl ether or O
Allyl aryl ether

1 2 1 2
3 3
O O -bond to
-bond to be formed
be broken 3
1 3 1
2 2

taut
O HO
O H

Cope rearrangement
2 1 2
1 3 3

R 1 R 1 3
3 2
2

Oxy-Cope rearrangement
2 1 2 2
1 1
3 3 taut 3

HO 1 3
HO 1 3 O 1 3 Suprafacial
2 2 2
 Sigmatropic Notation
Numbers in brackets refer to the two groups
connected by the s bond and designate the
positions in those groups to which migration
occurs
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

Based on McMurry, Organic

Chemistry, Chapter 30, 6th edition, 86
(c) 2003
 Sigmatropic Stereospecificity:
Suprafacial and Antarafacial
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

Based on McMurry, Organic

Chemistry, Chapter 30, 6th edition, 87
(c) 2003
Consider the transition state of the reaction,

Sigmatropic rearrangements have cyclic transition

states

Rearrangement must be suprafacial if the transition

state has six or fewer atoms in the ring
Stereochemical Rules of Sigmatropic
Rearrangements
Electron Pairs Thermal Photochemical
Reaction Reaction
Even Number Antarafacial Suprafacial
Odd Number Suprafacial Antarafacial

H
H
H
H

ANTARA
SUPRA Based on McMurry, Organic
Chemistry, Chapter 30, 6th edition, 89
(c) 2003
30.9 Some Examples of Sigmatropic
Rearrangements
A [1,5] sigmatropic rearrangement involves
three electron pairs (two bonds and one
bond)
Orbital-symmetry rules predict a suprafacial
reaction
5-methylcyclopentadiene rapidly rearranges at
room temperature

Based on McMurry, Organic

Chemistry, Chapter 30, 6th edition, 90
(c) 2003
Another Example of a Sigmatropic
Rearrangement
Heating 5,5,5-trideuterio-(1,3Z)-pentadiene
causes scrambling of deuterium between
positions 1 and 5

Based on McMurry, Organic

Chemistry, Chapter 30, 6th edition, 91
(c) 2003
[1,5] Rearrangement (H-shift)

Suprafacial H
5 5
1 1 4 H
H 4 H
-bond to
be broken 1 3 1 3
2 2

No. of electrons Reactions in the ground state Reactions in exited state

(termal) (Photochem.)
4n Antarafacial Suprafacial

4n + 2 Suprafacial Antarafacial

[1,3] Rearrangement (H-shift)

h
Suprafacial H
H H
H

Antarafacial

Too strained TS#

Ene reaction
 1.

2.