Pericyclic Reactions

Organic Chemistry
Sixth Edition
Janice Gorzynski
Smith
University of Hawai’I

Chapter 25
Lecture Outline
Prepared by Andrea
Leonard
University of Louisiana
at Lafayette
• ©2020 McGraw-Hill Education. All rights reserved. Authorized only for instructor use in the classroom. No reproduction or further distribution
©2020 McGraw-Hill Education.
permitted without the prior written consent of McGraw-Hill Education.
1
 Types of
Pericyclic
Reactions
A pericyclic reaction is a concerted reaction that
proceeds through a cyclic transition state.
Pericyclic reactions require light or heat and are
completely stereospecific.
• A particular stereoisomer of the reactant
forms a particular stereoisomer of the
product.
There are three categories of pericyclic reactions:
• Electrocyclic reactions
• Cycloadditions
• Sigmatropic rearrangements

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 Electrocyclic Reactions

An electrocyclic ring closure is an intramolecular reaction

that forms a cyclic product containing one more σ bond and
one fewer π bond than the reactant.

An electrocyclic ring opening is a reaction in which a σ

bond of a cyclic product is cleaved to form a conjugated
product with one more π bond.

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 Cycloaddition Reactions
A cycloaddition is a reaction between 2 compounds with π
bonds to form a cyclic product with two new σ bonds.

A sigmatropic rearrangement is a reaction in which a σ

bond is broken in the reactant, the π bonds rearrange, and
a σ bond is formed in the product.

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 Molecular
Orbitals
Molecular orbital (MO) theory describes
bonds as the mathematical combination
of atomic orbitals that forms a new set of
orbitals called molecular orbitals.
The number of atomic orbitals used
equals the number of MO’s formed.
The π bond in ethylene is formed by side-
by-side overlap of two p orbitals on
adjacent carbons.

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 Two p orbitals can combine in two different ways:
Molecular • When similar phases overlap, a π bonding MO results.

Orbitals of • When opposite phases overlap, a π∗ antibonding MO results.

Ethylene A destabilizing node between the orbitals occurs when two p

orbitals of opposite phase combine.

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 Molecular Orbitals of 1,3-Butadiene

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 Molecular Orbitals of 1,3-
Butadiene-1

The two π bonds of 1,3 butadiene are formed by

overlap of four p orbitals on adjacent carbons.
Four molecular orbitals are formed:
• 2 bonding molecular orbitals; and
• 2 anti-bonding molecular orbitals.
Bonding molecular orbitals are lower energy than
the p orbitals that combine to form them.
Anti-bonding molecular orbitals are higher energy
than the p orbitals that combine to form them.
As the number of nodes increases, the energy of
the molecular orbital increases.

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 HOMO and LUMO

The highest energy orbital that contains electrons

is called the highest occupied molecular orbital
(HOMO).
The lowest energy orbital that contains no
electrons is called the lowest unoccupied
molecular orbital (LUMO).
Thermal reactions utilize reactants in their ground
state electronic configuration.
When π-bonding molecules absorb light of
appropriate energy, an electron is promoted from
the HOMO to the LUMO.
Photochemical reactions occur with reactants in
this excited state.

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 HOMO and LUMO-1

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 The three π bonds of 1,3,5-
hexatriene are formed by overlap of
six p orbitals on six adjacent carbons.

Molecular Three bonding molecular orbitals and

three anti-bonding molecular orbitals
Orbitals of are formed.
1,3,5- In the ground state, the six p
Hexatriene electrons fill the three bonding
orbitals.

In the excited state, there is one

electron in the HOMO and one
electron in the LUMO.

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 Electrocyclic Reactions-1
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 form a conjugated polyene.

Use curved arrows and begin at a π bond.

Move the p electrons to an adjacent C—C bond and
continue in a cyclic fashion.
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 Stereochemistry of Electrocyclic
Reactions
Electrocyclic reactions are completely stereospecific.

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 Stereochemistry and Reaction
Conditions
The stereochemistry of the product of an electrocyclic
reaction depends on whether the reaction is carried out
under thermal or photochemical reaction conditions.

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 Stereochemistry and Orbital
Symmetry
Examine the HOMO of Determine if the p
the acyclic conjugated orbitals on the terminal
polyene that is either carbons have like
the reactant or product phases on the same
of an electrocyclic side or on opposite
reaction. sides.

An electrocyclic reaction occurs only when like phases of orbitals

can overlap to form a bond. This is called symmetry allowed.
An electrocyclic reaction cannot occur between lobes of opposite
phase. This is a symmetry forbidden reaction.
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 Modes of Rotation

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 In thermal reactions we consider the HOMO of the ground state
Thermal electronic configuration.

Rotation occurs in a disrotatory fashion for a conjugated

Electrocyclic polyene with an odd number of π bonds.

Reactions Cyclization occurs in a disrotatory fashion since the HOMO has

like phases on the same side of the molecule.

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 Rotation occurs in a conrotatory fashion for a
Thermal conjugated polyene with an even number of π
bonds.
Electrocyclic Cyclization occurs in a conrotatory fashion
Reactions-1 because the HOMO of the conjugated diene has
like phases on opposite sides of the molecule.

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 Since electrocyclic reactions are reversible,
ring-opening reactions follow the same rules as
Electrocyclic ring closures.

Ring-Opening Electrocyclic ring opening which forms a diene

with an even number of π bonds occurs in a
conrotatory fashion.

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 In photochemical reactions, we must consider the orbitals of the HOMO of
the excited state to determine the course of the reaction.

Photochemical As a photon is absorbed, an electron from the ground state HOMO is excited
to the ground state LUMO.

Electrocyclic This orbital is now the excited state HOMO.

The excited state HOMO will have the opposite orientation of the terminal p
Reactions orbitals as the ground state HOMO.
The method of ring closure of a photochemical electrocyclic reaction is
opposite to that of a thermal reaction for the same number of π bonds.

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 Electrocyclic Reactions-2
Photochemical electrocyclic reactions occur in a disrotatory
fashion for a conjugated polyene with an even number of p
bonds.

Table 25.1 Woodward-Hoffmann Rules for Electrocyclic Reactions

Number of π bonds Thermal reaction Photochemical reaction
Even Conrotatory Disrotatory
Odd Disrotatory Conrotatory

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 A cycloaddition is a reaction between two compounds with π
bonds to form a cyclic product with two new σ bonds.

Cycloaddition They are concerted, stereospecific reactions controlled by the

symmetry of the molecular orbitals.
Reactions-1 The Diels-Alder reaction is a thermal [4+2] cycloaddition that
occurs between a diene with 4 π electrons and an alkene
(dienophile) with 2 π electrons.

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 Photochemical Cycloaddition
Reactions
A photochemical [2+2] cycloaddition occurs between two
alkenes, each with 2 π electrons to form a cyclobutane.
Thermal [2+2] cycloadditions do not take place.

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 To understand cycloaddition reactions, examine the p orbitals of
the terminal carbons of both reactants.
Orbital Bonding can take place only when like phases of both sets of p
Symmetry and orbitals can combine.

Cycloadditions 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.

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 Antarafacial Cycloadditions
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.

Due to geometrical restraints of small rings, cycloadditions

that form 4- or 6-membered rings must take place by
suprafacial pathways.

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 Molecular Orbital Interactions

Cycloaddition The HOMO of one

involves donation of reactant donates Examine the course
electron density electrons to the of a [4+2]
from one reactant to LUMO of the other cycloaddition.
another. reactant.

Thermal cycloadditions involving an odd number of π

bonds proceed by a suprafacial pathway.
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 Stereochemistry Because Diels-Alder reactions follow a
concerted, suprafacial pathway, the
of Diels-Alder stereochemistry of the diene is retained in the
Reactions Diels-Alder product.

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 [2+2] Cycloadditions

In a thermal [2+2]
[2+2] cycloadditions do cycloaddition, like
not occur under thermal phases of the p orbitals
conditions, but do take on only one set of
place photochemically. terminal carbons can
overlap.

For like phases to overlap on the other terminal carbon, the

molecule would have to twist for an antarafacial pathway, which
cannot occur to form small rings.
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 In photochemical [2+2] cycloaddition, light energy promotes an
electron from the ground state HOMO to form the excited state
Photochemical HOMO.

[2+2] The interaction of the excited state HOMO with the LUMO of the
second alkene allows for overlap of both sets of p orbitals.
Cycloadditions Photochemical cycloadditions involving an even number of π
bonds proceed by a suprafacial pathway.

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 Table 25.2 Woodward-
Summary of Hoffmann Rules for
Cycloaddition
Cycloaddition Reactions Reactions

Number of π Thermal Photochemical

bonds reaction reaction
Even Antarafacial Suprafacial
Odd Suprafacial Antarafacial

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 Sigmatropic Rearrangements
A sigmatropic rearrangement is an intramolecular pericyclic
reaction is which a σ bond is broken in a reactant, the π
bonds rearrange, and a new σ bond is formed in the
product.
• The number of π bonds in reactant and product is constant.
• The σ bonds broken and formed are both allylic.

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 Designating Sigmatropic
Rearrangements
Sigmatropic rearrangements are characterized by a set of
numbers in brackets to indicate the location of the new σ
bond relative to the broken σ bond.
• Locate the σ bond broken in the reactant and label both atoms in
the bond with “1’s”.
• Locate the new σ bond in the product and count the number of
atoms from the broken bond to the new bond for each fragment.
• Place both numbers in brackets with the lower number first.

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 Sigmatropic
Rearrangements and
Orbital Symmetry

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 Symmetry Rules Sigmatropic
Rearrangements
Table 25.3 Woodward-Hoffmann Rules for Sigmatropic Rearrangements
Number of electron pairs Thermal reaction Photochemical reaction
Even Antarafacial Suprafacial
Odd Suprafacial Antarafacial

For example, a [1,5] sigmatropic rearrangement involves 3

electron pairs, one from the σ bond that is broken and two
from the π bonds that rearrange.

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 [3,3] Sigmatropic Rearrangements
There are two widely used [3,3] sigmatropic
rearrangements in organic synthesis:
• Cope rearrangement is the rearrangement of a 1,5-diene to an
isomeric 1,5-diene.

• Claisen rearrangement is the rearrangement of an unsaturated

ether to a γ,δ-unsaturated carbonyl compound.

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 Oxy-Cope Rearrangement
The oxy-Cope rearrangement is an especially powerful variation of a Cope rearrangement using an
unsaturated alcohol.

[3,3] Sigmatropic rearrangement forms an enol initially, which then tautomerizes to form a carbonyl group.

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 Anionic oxy-Cope rearrangement often gives
high yields under very mild reaction conditions.
Anionic Oxy- The unsaturated alcohol is treated with strong
Cope base to form an alkoxide.
[3,3] Sigmatropic rearrangement then yields a
Rearrangement resonance-stabilized enolate.
This is protonated to form a carbonyl product.

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 Claisen Rearrangement

Claisen rearrangement is a [3,3] sigmatropic rearrangement of

an unsaturated ether.
With allyl vinyl ethers, a γ,δ-unsaturated carbonyl compound is
formed directly by the concerted rearrangement.

With allyl aryl ethers, a cylohexadienone intermediate forms,

which tautomerizes into a phenol.

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 Summary of Rules for Pericyclic
Reactions
A thermal reaction involving an even number of electron
pairs is conrotatory and suprafacial.
• If one of the reaction conditions changes – the stereochemistry of
the reaction changes.
• If both reaction conditions change, the stereochemistry does not
change.

Table 25.4 Summary of the Stereochemical Rules for Pericyclic Reactions

Reaction conditions Number of electron pairs Stereochemistry
Thermal Even Conrotatory or antrafacial
Odd Disrotatory or suprafacial
Photochemical Even Disrotatory or suprafacial
Odd Conrotatory or antarafacial

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