30.

Orbitals and Organic

Chemistry: Pericyclic
Reactions
Based on McMurrys Organic Chemistry, 6th
edition

Pericyclic Reactions What Are?

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

Based on McMurry, Organic Chemistry, Chapter

30, 6th edition, (c) 2003

30.1 Molecular Orbitals of Conjugated

Systems
A conjugated diene or polyene has alternating double

and single bonds

Bonding MOs are lower in energy than the isolated p
atomic orbitals and have the fewest nodes
Antibonding MOs are higher in energy
See Figure 30.1 for a diagram

Based on McMurry, Organic Chemistry, Chapter

30, 6th edition, (c) 2003

1,3,5-Hexatriene
Three double bonds and six MOs
Only bonding orbitals, 1, 2, and 3, are filled in the

ground state
On irradiation with ultraviolet light an electron is
promoted from 3 to the lowest-energy unfilled orbital
(4*)
This is the first (lowest energy) excited state
See the diagram in Figure 30.2

Based on McMurry, Organic Chemistry, Chapter

30, 6th edition, (c) 2003

30.2 Molecular Orbitals and Pericyclic

Reactions
If the symmetries of both reactant and product

orbitals match the reaction is said to be symmetry

allowed under the Woodward-Hoffmann Rules
(these relate the electronic configuration of reactants
to the type of pericyclic reaction and its
stereochemical imperatives)
If the symmetries of reactant and product orbitals do
not correlate, the reaction is symmetry-disallowed
and there no low energy concerted paths
Fukuis approach: we need to consider only the
highest occupied molecular orbital (HOMO) and the
lowest unoccupied molecular orbital (LUMO), called
the frontier orbitals
Based on McMurry, Organic Chemistry, Chapter
30, 6th edition, (c) 2003

30.3 Electrocyclic Reactions

These are pericyclic processes that involves the

cyclization of a conjugated polyene

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

Based on McMurry, Organic Chemistry, Chapter

30, 6th edition, (c) 2003

Example: Electrocyclic Interconversions With

Octatriene

Based on McMurry, Organic Chemistry, Chapter

30, 6th edition, (c) 2003

Example: Electrocyclic Interconversions with

Dimethylcyclobutene

Based on McMurry, Organic Chemistry, Chapter

30, 6th edition, (c) 2003

The Signs on the Outermost Lobes

Must Match to Interact
The lobes of like sign can be either on the same side

or on opposite sides of the molecule.

For a bond to form, the outermost lobes must rotate
so that favorable bonding interaction is achieved

Based on McMurry, Organic Chemistry, Chapter

30, 6th edition, (c) 2003

Disrotatory Orbital Rotation

If two lobes of like sign are on the same side of the

molecule, the two orbitals must rotate in opposite

directionsone clockwise, and one counterclockwise
Woodward called this a disrotatory (dis-roh-tate-oree) opening or closure

Based on McMurry, Organic Chemistry, Chapter

30, 6th edition, (c) 2003

10

Conrotatory Orbital Rotation

If lobes of like sign are on opposite sides of the

molecule: both orbitals must rotate in the same

direction, clockwise or counterclockwise
Woodward called this motion conrotatory (con-rohtate-or-ee)

Based on McMurry, Organic Chemistry, Chapter

30, 6th edition, (c) 2003

11

30.4 Stereochemistry of Thermal

Electrocyclic Reactions
Determined by the symmetry of the polyene

HOMO
The ground-state electronic configuration is
used to identify the HOMO
(Photochemical reactions go through the
excited-state electronic configuration )

Based on McMurry, Organic Chemistry, Chapter

30, 6th edition, (c) 2003

12

Ring Closure of Conjugated Trienes

Involves lobes of like sign on the same side of the

molecule and disrotatory ring closure

Based on McMurry, Organic Chemistry, Chapter

30, 6th edition, (c) 2003

13

Contrast: Electrocyclic Opening to

Diene
Conjugated dienes and conjugated trienes react with

opposite stereochemistry
Different symmetries of the diene and triene HOMOs
Dienes open and close by a conrotatory path
Trienes open and close by a disrotatory path

Based on McMurry, Organic Chemistry, Chapter

30, 6th edition, (c) 2003

14

30.5 Photochemical Electrocyclic

Reactions
Irradiation of a polyene excites one electron from

HOMO to LUMO
This causes the old LUMO to become the new
HOMO, with changed symmetry
This changes the reaction stereochemistry
(symmetries of thermal and photochemical
electrocylic reactions are always opposite)

Based on McMurry, Organic Chemistry, Chapter

30, 6th edition, (c) 2003

15

Rules for Electrocyclic Reactions

Based on McMurry, Organic Chemistry, Chapter

30, 6th edition, (c) 2003

16

30.6 Cycloaddition Reactions

Two unsaturated molecules add to one another,

yielding a cyclic product

The DielsAlder cycloaddition reaction is a pericyclic
process that takes place between a diene (four
electrons) and a dienophile (two electrons) to yield
a cyclohexene product Stereospecific with respect to
substituents

Based on McMurry, Organic Chemistry, Chapter

30, 6th edition, (c) 2003

17

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

Based on McMurry, Organic Chemistry, Chapter

30, 6th edition, (c) 2003

18

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)

Based on McMurry, Organic Chemistry, Chapter

30, 6th edition, (c) 2003

19

30.7 Stereochemistry of
Cycloadditions
HOMO of one reactant combines with LUMO of other
Possible in thermal [4 +2] cycloaddition

Based on McMurry, Organic Chemistry, Chapter

30, 6th edition, (c) 2003

20

[2+2] Cylcoadditions
Only the excited-state HOMO of one alkene and the

LUMO can combine by a suprafacial pathway in the

combination of two alkenes

Based on McMurry, Organic Chemistry, Chapter

30, 6th edition, (c) 2003

21

Formation of Four-Membered Rings

Photochemical [2 + 2] cycloaddition reaction occurs

smoothly

Based on McMurry, Organic Chemistry, Chapter

30, 6th edition, (c) 2003

22

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

Based on McMurry, Organic Chemistry, Chapter

30, 6th edition, (c) 2003

23

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, (c) 2003

24

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, (c) 2003

25

Stereochemical Rules of Sigmatropic

Rearrangements
Electron Pairs Thermal
Reaction
Even Number Antarafacial
Odd Number Suprafacial

Photochemical
Reaction
Suprafacial
Antarafacial
H
H

H
H

SUPRA

Based on McMurry, Organic Chemistry, Chapter

30, 6th edition, (c) 2003

ANTARA

26

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, (c) 2003

27

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, (c) 2003

28

Orbital Picture of a Suprafacial [1,5] H

Shift

Based on McMurry, Organic Chemistry, Chapter

30, 6th edition, (c) 2003

29

Cope and Claisen Rearrangements are

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

Based on McMurry, Organic Chemistry, Chapter

30, 6th edition, (c) 2003

30

Suprafacial [3,3] Cope and Claisen

Rearrangements
Both involve reorganization of an odd number of

electron pairs (two bonds and one bond)

Both react by suprafacial pathways

Based on McMurry, Organic Chemistry, Chapter

30, 6th edition, (c) 2003

31

30.10 A Summary of Rules for

Pericyclic Reactions

Based on McMurry, Organic Chemistry, Chapter

30, 6th edition, (c) 2003

32