Pericyclic Reactions

Dr. Bijan Mohon Chaki

Associate Professor
Department of Chemistry
Begum Rokeya University, Rangpur
 Course : CHEM 3224
Theory of Organic Chemistry
3 Credits; 3 Class Hours/Week
Marks :100 (Cont. Ass. 50% + Final Ass. 50%)

1. Kinetics, energetic and investigation of organic reaction mechanism :

Kinetics and Energetics: Reaction rate, reversible reactions, mechanistic
implications from rate law, transition state theory, energy of activation,
entropy of activation. Classes of reaction mechanism, investigation of
reaction mechanism: isolation and identification of products, salt effects,
study of intermediates, trapping and detection of intermediates, crossover
experiment, kinetic, isotopic and stereochemical studies.

2. Orbital symmetry and Pericyclic Reactions :

LCAO’s theory and MO’s theory illustration with 1,3-butadiene, allyl
system and 1,3,5- hexatriene. HOMO, LUMO, Electrocyclic and
cycloaddition both in thermal and photochemical methods, stereochemistry
and mechanisms. Woodward-Hofmann rule, sigmatropic changes (both
carbon and H-shift), Cope and Claisen rearrangements & stereochemistry.
3. Free radical reaction :
Definitions, generation and detection of free radicals. Long and short lived free
radicals, configuration of free radicals, types of free radical reactions, examples &
mechanism. Autoxidation, radical initiators and radical scavengers.

4. Photochemistry :
Light absorption, fluorescence and phosphorescence, generation of singlet and
triplet states, energy transfer and photosensitization reactions, quantum yield.
Example of photochemical reaction: photorearrangement, photoaddition,
photosubstitution, photooxidation/reduction, photocyclization, photoelimination,
Norrish I & II type reactions, photochemistry of aromatic compounds, flash
photolysis.

Recommended Books:
1. J. March : Advanced Organic Chemistry
2. R.T. Morrison and R.N. Boyd : Organic Chemistry
3. E.S. Gould : Mechanism and Structure in Organic
Chemistry
4. E.L Eliel : Stereochemistry of Carbon Compounds
5. F. A. Carey & R. J. Sundberg : Advanced Organic Chemistry
6. J. Clayden, N. Greevs & S. warren : Organic Chemistry
Pericyclic Reactions :

LCAO’s theory and MO’s theory illustration with 1,3-butadiene, allyl

system and 1,3,5- hexatriene. HOMO, LUMO, Electrocyclic and
cycloaddition both in thermal and photochemical methods, stereochemistry
and mechanisms. Woodward-Hofmann rule, sigmatropic changes (both
carbon and H-shift), Cope and Claisen rearrangements & stereochemistry.

Book References:
1. Advanced Organic Chemistry (5th Ed., Part A)- Francis A. Carey and
Richard J Sundberg.

2. Organic Chemistry (6th Ed.)- R.T. Morrison and R.N. Boyd

3. Organic Chemistry (3rd Ed.)- Janice G. Smith

After studying this module, you shall be able to

 Know what do we mean by pericyclic reaction.

 Learn the ways to bond making and breaking in a cyclic molecular
formation/deformation.
 Identify the reactants, products and intermediates involved in a reaction
Organic Reactions

Polar Reaction
Free Radical Reaction

Pericyclic Reactions
A number of useful reactions
occur in one-step processes
that do not form reactive
intermediates, the pericyclic
reaction
 Pericyclic Reactions
 A pericyclic reactions : result of reorganizing the electrons in the
reactant(s).
 Electrons move round a circle and there are no positive or
negative charges on any intermediates— indeed, there are no
intermediates at all. This type of reaction is called pericyclic
reactions.
 Thus: A pericyclic reaction is a concerted reaction that proceeds
through a cyclic transition state.
 The common feature is a concerted mechanism involving a cyclic
TS with continuous electronic reorganization.

The formation of stable – benzene like structure in the intermediate.

 Three striking things matter

1. Number of electrons involved

2. Stereospecificity

3. Conditions: heat (Δ) vs. light (hυ)

Molecular Orbital and Orbital Symmetry (for 1)
Pericyclic reactions require light or heat and are
completely stereospecifc; that is, a single stereoisomer of
the reactant forms a single stereoisomer of the product. (for
2
Categories of Pericyclcic Reaction:

1. Electrocyclic Reactions

2. Cycloaddition Reactions

3. Sigmatropic Rearrangement
 Molecular Orbital and Orbital Symmetry

The overlap of p atomic orbitals to form π-molecular orbitals can be

described mathematically using quantum mechanics.
Two in-phase p atomic orbitals interact, a covalent bond is formed
Two out-of-phase atomic orbitals interact, a node is created between
the two nuclei
An electron goes into the available molecular orbital with the lowest
energy, and only two electrons can occupy a particular molecular
orbital
Orbitals are conserved—two atomic orbitals combine to produce two
molecular orbitals
Four atomic orbitals combine to produce four molecular orbitals,
six atomic orbitals combine to produce six molecular orbitals
(LCAO-Linear Combination of Atomic Orbitals)
 Recall---LCAO

LCAO concept introduced in Molecular orbital theory.

To overcome the problem of being unable to solve the Schrödinger

equation for a system with more than one electron.

According to LCAO atomic orbitals interfere constructively and

destructively to form molecular orbitals.

If an electron can be found in an atomic orbital belonging to atom A

and also to atom B, then the overall wave function is a superposition
of the two orbitals.
 Recall---LCAO

BMO-bonding molecular orbitals are formed when

 wave functions of atomic orbitals are added-

Ψା = ߶஺ + ߶஻

 There occurs constructive interference of atomic orbitals-

 Atomic orbitals overlap each other in phase.

Properties of BMO
Electron density is located between the nuclei reduces repulsion
between them reduces the energy of the molecular orbital stabilizes
the system
The energy of BMO is always less than the participating atomic
orbitals
 Recall---LCAO

ABMO-antibonding molecular orbitals are formed when

 wave functions of atomic orbitals are subtracted-

Ψି = ߶஺ - ߶஻

 There occurs destructive interference of atomic orbitals-

 Atomic orbitals overlap without phase.

Properties of ABMO
Electron density is located far away from the two nuclei which
creates a nodal plane between the nuclei-
Increases repulsion between them-
Increases the energy of the system-
Destabilizes the molecule
The energy of ABMO is higher than that of parent atomic orbitals.
 Ethylene
The π bond in ethylene (CH2= CH2) is formed by side-by-side overlap of two p orbitals on
adjacent carbons. Two p orbitals can combine in two different ways. As shown in Figure C.1,
when two p orbitals of similar phase overlap, a " bonding molecular orbital (designated as Ψ1)
results.
Two electrons occupy this lower-energy bonding molecular orbital. When two p orbitals of
opposite phase combine, a π* antibonding molecular orbital (designated as Ψ2*) results. A
destabilizing node occurs when two orbitals of opposite phase combine.
Similarly, 1,3-butadiene, and 1,3,5-hexatriene, molecules that contain two and three π
bonds, respectively.

The ground-state
HOMO and the
excited-state
HOMO always
have opposite
symmetries—one
is symmetric and
the other is
asymmetric
The four π molecular orbitals of 1,3-butadiene
 In 1,3-butadiene,
 In the ground-state electronic arrangement, the four π electrons occupy the two
bonding molecular orbitals.

HOMO & LUMO

 The highest energy orbital that contains electrons is called the highest occupied
molecular orbital (HOMO). In the ground state of 1,3-butadiene, Ψ2 is the HOMO.

 The lowest energy orbital that contains no electrons is called the lowest
unoccupied molecular orbital (LUMO). In the ground state of 1,3-butadiene, Ψ2* is
the LUMO.
 The thermal reactions utilize reactants in their ground state electronic configuration.

 When 1,3-butadiene absorbs light of appropriate energy, an electron is promoted

from Ψ2 (the HOMO) to Ψ3* (the LUMO) to form a higher energy electronic
configuration, the excited state.

 In the excited state, the HOMO is now Ψ3*. In the photochemical reactions, the
reactant is in its excited state. As a result, the HOMO is Ψ3* and the LUMO is Ψ4*
for 1,3-butadiene.
Let’s talk on 1,3,5-Hexatriene

 Number of bonds of 1,3,5-hexatriene (CH2=CH–CH=CH–CH=CH2) ???

 How many p orbitals and how many ways are involved in overlapping???

As shown in Figure C.3,

 Name the molecular orbitals (MOs) formed.

 How many bonding molecular orbitals, and antibonding molecular orbitals

and what are they???

 Which MO is HOMO and LUMO???

 In the excited state, which MO is HOMO and LUMO???

 Electrocyclic Reactions
 An electrocyclic reaction is a reversible reaction that involves ring closure of a
conjugated polyene to a cycloalkene, or ring opening of a cycloalkene to a conjugated
polyene.

 For example, Ring closure of 1,3,5-hexatriene forms 1,3-cyclohexadiene.

 It is an intramolecular reaction in which a new (σ-sigma) bond is formed between the

ends of a conjugated (pi) system.

 On the other hand, ring opening of cyclobutene forms 1,3-butadiene, a product with
one fewer σ- bond and one more π-bond than the reactant.
Use curved arrows and draw the product of each electrocyclic reaction:
Stereochemistry and Orbital Symmetry:

Electrocyclic reactions are completely stereospecific.

For example, (i) Ring closure of (2E,4Z,6E)-2,4,6-octatriene yields a single product with cis
methyl groups on the ring.

(ii) Ring opening of cis-3,4-dimethylcyclobutene forms a single conjugated diene with one Z
alkene and one E alkene.
Thermal(Thermochemical) and Photochemical Electrocyclic Reactions:

Electrocyclic reaction depends on whether the reaction is carried out under thermal or
photochemical reaction conditions—that is, with heat or light, respectively.

Cyclization of (2E,4E)-2,4-hexadiene with heat forms a cyclobutene with trans methyl

groups, whereas cyclization with light forms a cyclobutene with cis methyl groups.
Thermal(Thermochemical) and Photochemical Electrocyclic Reactions:

 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.
Thermal(Thermochemical) and Photochemical Electrocyclic Reactions:

 To form a bond, the p orbitals on the terminal carbons must rotate so that like phases can
interact to form the new σ bond.
 Two modes of rotation are possible: Conrotatory and Disrotatory.

 When like phases of the p orbitals are on the same side of the molecule, the two orbitals
must rotate in opposite directions—one clockwise and one counter clockwise.

 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 direction—both clockwise or both counterclockwise.
 Rotation in the same direction is said to be conrotatory.
Thermal(Thermochemical) Electrocyclic Reactions:

 Thermal electrocyclic reactions occur in a disrotatory fashion for a conjugated polyene

with an odd number of π bonds.
 In a thermal reaction, we consider the HOMO of the ground state electronic
configuration. Rotation occurs in a disrotatory or conrotatory fashion so that like phases of
the p orbitals on the terminal carbons of this molecular orbital combine.
Two examples illustrate different outcomes.
 Thermal electrocyclic ring closure of (2E,4Z,6E)-2,4,6-octatriene yields a single product
with cis methyl groups on the ring.

 Cyclization occurs in a disrotatory fashion because the HOMO of a conjugated triene

has like phases of the outermost p orbitals on the same side of the molecule. A disrotatory
ring closure is symmetry allowed because like phases of the p orbitals overlap to form the
new σ-bond of the ring. In the disrotatory ring closure, both methyl groups are pushed
down (or up), making them cis in the product..
Thermal(Thermochemical) Electrocyclic Reactions:

 In contrast, thermal electrocyclic reactions occur in a conrotatory fashion for a

conjugated polyene with an even number of π bonds.
 Thermal electrocyclic ring closure of (2E,4E)-2,4-hexadiene forms a cyclobutene with
trans methyl groups.

 Cyclization occurs in a conrotatory fashion because the HOMO of a conjugated

diene has like phases of the outermost p orbitals on opposite sides of the
molecule. A conrotatory ring closure is symmetry allowed because like phases of
the p orbitals overlap to form the new σ- bond of the ring. In the conrotatory ring
closure, one methyl group is pushed down and one methyl group is pushed up,
making them trans in the product.
Thermal(Thermochemical) Electrocyclic Reactions:

 Since electrocyclic reactions are reversible, electrocyclic ring-opening reactions follow

the same rules as electrocyclic ring closures.

 Thus, thermal ring opening of cis-3,4-dimethylcyclobutene, which ring opens to a diene

with an even number of “ bonds occurs in a conrotatory fashion to form (2E,4Z)-2,4-
hexadiene as the only product.
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 π bonds.

 Photochemical electrocyclic ring closure of (2E,4Z,6E)-2,4,6-octatriene yields a cyclic

product with trans methyl groups on the ring.

Thus, photochemical electrocyclic reactions occur in a conrotatory fashion for a

conjugated polyene with an odd number of π bonds.
Photochemical Electrocyclic Reactions:

 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 π bonds.
 Thus, photochemical electrocyclic reactions occur in a disrotatory fashion for a conjugated
polyene with an even number of π bonds.
 Cycloaddition Reactions:

 A cycloaddition is a reaction between two compounds with “ bonds to form a cyclic product
with two new σ bonds. Like electrocyclic reactions, cycloadditions are concerted,
stereospecific reactions, and the course of the reaction is determined by the symmetry of the
molecular orbitals of the reactants.
 thermal conditions or light photochemical conditions. Cycloadditions are identified by the
number of “ electrons in the two reactants.
 The Diels–Alder reaction is a thermal [4 + 2] cycloaddition that occurs between a diene with
four π electrons and an alkene (dienophile) with two " electrons

 A photochemical [2 + 2] cycloaddition occurs between two alkenes, each with two π

electrons, to form a cyclobutane. Thermal [2 + 2] cycloadditions do not take place.
 Cycloaddition Reactions:

Orbital Symmetry and Cycloadditions

 To understand cycloaddition reactions, we examine the p orbitals of the terminal carbons of
both reactants. Bonding can take place only when like phases of both sets of p orbitals can
combine.
Two modes of reaction are possible.
 A suprafacial cycloaddition occurs when like phases of the p orbitals of both reactants are on
the same side of the π system, so that two bonding interactions result.

An antarafacial cycloaddition occurs

when one π system must twist to align
like phases of the p orbitals of the
terminal carbons of the reactants.
 Cycloaddition Reactions:

 Since cycloaddition involves the donation of electron density from one reactant to another,
one reactant donates its most loosely held electrons—those occupying its HOMO—to a
vacant orbital that can accept electrons—the LUMO—of the second reactant. The HOMO of
either reactant can be used for analysis.
 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, let’s 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 [4 + 2]cycloaddition

 Thermal cycloadditions involving an odd number of π bonds proceed by a suprafacial

pathway.
 Cycloaddition Reactions:

 Because a Diels–Alder reaction follows a concerted, suprafacial pathway, the

stereochemistry of the diene is retained in the Diels–Alder 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)-2,4-hexadiene with ethylene forms a cyclohexene with
trans substituents.

 Thermal [4 + 2]cycloaddition
 Cycloaddition Reactions:

 [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 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.
 Cycloaddition Reactions:
 [2 + 2] Cycloadditions
 Cycloaddition Reactions:

 In a photochemical [2 + 2] cycloaddition, light energy promotes an electron from the ground

state HOMO to form the excited state HOMO. Interaction of 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.

 Photochemical cycloadditions involving an even number of “ bonds proceed by a suprafacial

pathway.
 Woodward–Hoffmann rules for cycloaddition reactions
 Cycloaddition Reactions:

 Types of Diels–Alder Reactions

 Normal electron demand = HOMO of diene + LUMO of dienophile
 Inverse electron demand = HOMO of dienophile + LUMO of diene
 Cycloaddition Reactions:

 Specific Rules Governing the Diels–Alder Reaction

 1. The Diels-Alder reaction is inherently stereospecific
Ex: A cis dienophile will generate a ring with cis substitution, while a trans dienophile will
generate a ring with trans substitution:

2. In order for a Diels-Alder reaction to occur, the diene molecule must adopt what is called
the s-cis conformation:
 Cycloaddition Reactions:

 The s-cis conformation is higher in energy than the s-trans conformation, due to steric
hindrance. For some dienes, extreme steric hindrance causes the s-cis conformation to be
highly strained, and for this reason such dienes do not readily undergo Diels-Alder
reactions.

3. A cyclic dienophile forms a bicyclic product. A bicyclic system in which the two rings
share a common C – C bond is called a fused ring system. The two H atoms at the ring
fusion must be cis, because they were cis in the starting dienophile. A bicyclic system of this
sort is said to be cis-fused.
 Cycloaddition Reactions:

4. When endo and exo products are possible, the endo product is preferred.
Here, we see another element of stereopecificity: Diels-Alder reactions with cyclic dienes
favor the formation of bicyclic structures in which substituents are in the endo position.
 Cycloaddition Reactions:

4. When endo and exo products are possible, the endo product is preferred.

 A substituent on one bridge is endo if it is closer to the longer bridge that joins the two
carbons common to both rings.
 A substituent is exo if it is closer to the shorter bridge that joins the carbons together.
 Cycloaddition Reactions:

 In a Diels–Alder reaction, the endo product is preferred, as shown in two examples. To help
you distinguish endo and exo, remember that endo is under the newly formed six membered
ring.
 Cycloaddition Reactions:

 How endo and exo products are formed in the Diels–Alder reaction
 Sigmatropic Rearrangement:

 Reorganization of electrons attached by a σ-bond migrates to the other terminus of a

conjugated π -electron system, with a simultaneous shift of the π -electrons.
i.e. Reorganization of σ and π bonds (migration of a σ-bond)
 Number of σ and π bonds remains constant
 Classify by [m,n]-rearrangement or [m,n]-shift (m, n = number of atoms in fragment)
How It occur:
 If the migrating group remains associated with the same face of the conjugated system
throughout the reaction, the migration is termed suprafacial mode.
 If the migrating group moves to the opposite face of the system during the course of the
migration called antarafacial mode.
 (3,3) sigmatropic rearrangement
 (2,3) sigmatropic rearrangement
 (1,5) sigmatropic rearrangement

 (3,3) sigmatropic rearrangement:

 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 3
1 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 HO 1 3 O 1 3 Suprafacial
3 2
2 2
[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

Antarafacial

Too strained TS#

 Sigmatropic Rearrangement:

 (2,3) Sigmatropic rearrangement

 The starting material is a benzyl allyl ether and undergoes [2,3]-sigmatropic rearrangement
to make a new C–C σ bond at the expense of a C–O σ bond—a bad bargain this as the C–O
bond is stronger. The balance is tilted by the greater stability of the oxyanion in the product
than of the carbanion in the starting material. The new bond has a 2,3 relationship to the old
and the transition state is a fi ve-membered ring.
Sigmatropic Rearrangement:

John McMurry
 Sigmatropic Rearrangement:

 Sigmatropic rearrangernents, like electrocyclic reactions and cycloadditions , are controlled

by orbital symmetries . There are two possible modes of reaction : migration of a group
across the same face of the π system is called a suprafacial rearrangement, and migration of a
group from one face of the π system to the other face is called an antnraiacial rearrangement

John McMurry
 Sigmatropic Rearrangement:

 Some Sigmatropic rearrangernents: For example, S-methyl-l ,3-cyclopentadiene rapidly

rearranges at room temperature to yield a mixture of l-methyl- , 2-methyl-, and 5-methyl-
substituted products.

 As another example, heating 5,5,5-trideuterio- (l ,3Z)- l ,3-pentadiene causes scrambling of

deuterium between positions 1 and 5.

Source Book: John McMurry