AOR No10 (2016.7.

15)
Thermal Pericyclic Reaction Pericyclic Reactions

6.1 The Four Classes of Pericyclic Reactions

1. Cycloadditions (bimolecular)
Cheletropic reaction

Otto Paul Hermann Diels Kurt Alder

(1876 1954) (1902 1958) protection of diene

2. Electrocyclic reactions (Unimolecular) [1,7]-shift

-50 kJ/mol Mislow rearrangement

3. Sigmatropic rearrangement (Unimolecular) [2,3]-shift
Claisen rearrangement
[3,3]-shift
 4. Group transfer reaction (Bimolecular) 6.2 Evidence for the Concertedness of Bond Making and Breaking

ene reaction No intermediates

Diels-Alder reactions: exothermic

high negative entropy of activation, -150 to -200 J K-1 mol-1,
with a low enthalpy of activation

Sauer, Angew. Chem., Int. Ed. Engl. 1980, 19, 779

Metalla-ene reaction
Little effect by solvent polarity
Stereochemistry
Isotope effect Substituent effect

M = Li, Mg, Pd

[4 + 2]
6.3 Symmetry-allowed and Symmetry-forbidden Reaction

6.3.1 The Woodward-Hoffmann Rules Class by Class

6.3.1.1. Cycloadditions

[2 + 2]

Diels-Alder reaction: [4 + 2] cycloaddition

number of electrons
1,3-Dipolar cycloaddition Rule of cycloadditions
X,Y,Z,A,B = (C, N, O, S)

A thermal pericyclic cycloaddition is

allowed if the total number of electrons
involved can be expressed in the form
(4n+2), where n is an integer. If the total
10-electrons
number of electrons can be expressed in
[8 + 2] the form (4n) it is forbidden.

(4n + 2) electrons

[6 + 4]

Suprafacial-Suprafacial (4n + 2)
Suprafacial-Antarafacial 4n (allowed)
Antarafacial-Antarafacial

[14 + 2]

trans
Rule of cycloadditions
6.3.1.2 Electrocyclic Reactions 4n, 4n+2
Ring strain, aromaticity, stabilization of charge by substituent
If the total number of electrons involved
can be expressed in the form (4n+2),
where n is an integer, a thermal
pericyclic cycloaddition is symmetry
allowed when both components react in a
suprafacial manner (or both components
react in an antarafacial manner). If the
total number of electrons can be
expressed in the form (4n), it is allowed
if one of the components reacts in a
suprafacial manner and the other
antarafacial.

Stereochemistry
Woodward-Hoffman rule (1965)
Disrotatory ( ) and Conrotatory
Thermal electrocyclic reactions involving
a total number of electrons that can be
expressed in the form (4n+2) are
disrotatory, and thermal electrocyclic
reactions in which the total number of
electrons can be expressed in the form
(4n) are conrotatory

Robert Burns Woodward Roald Hoffmann

(1917 1979) 1937- )
Examples
6.3.1.3 Sigmatropic Rearrangements [1,5]

[1,n] H-shift (4n+2)

only

Sigmatropic rearrangements of hydrogen are

suprafacial if the total number of electrons is a
(4n+2) number and antarafacial if the total
number of electrons is a (4n) number.

2e 4e
H => C

When the total number of electrons is a (4n+2)

number, [1,n] sigmatropic rearrangements of
elements other than hydrogen are either suprafacial
with retention of configuration in the migrating Ref)
group or are antarafacial with inversion of Wagner-Meerwein rearrangement
configuration in the migrating group.

When the total number of electrons is a (4n) number,

[1,n] sigmatropic rearrangements of elements other
than hydrogen are either antarafacial with retention
of configuration in the migrating group or are
suprafacial with inversion of configuration in the
migrating group
Ref) Ref)

Beckmann rearrangement

Baeyer-Villiger

When the total number of electrons is a (4n+2)

Suprafacial [1,3]-shift Suprafacial [1,4]-shift number, [m,n]-sigmatropic rearrangements are
allowed if both migrations are suprafacial or both
antarafacial.

When the total number of electrons is a (4n)

number, [m,n]-sigmatropic rearrangements are
allowed if one migration is suprafacial and the
other antarafacial.
 (4n+2)
Ireland-Claisen rearrangement

Cope rearrangement

10 electrons
6.3.1.4 Group Transfer Reaction

Stevens rearrangement

When the total number of electrons is a (4n+2)

number, group transfer reactions are allowed
with all-suprafacial stereochemistry.
The Generalised Woodward-Hoffmann Rule 6.3.2.1 Cycloadditions

(1) which of these components is acting in a suprafacial manner and

which in an antarafacial manner?
1969
(1) in which of these components can the number of electrons be
expressed in the form (4q+2) and in which in the form (4r),
A ground-state pericyclic change is where q and r are integers?

symmetry allowed when the total

number of (4q+2)s and (4r)a
components is odd.
6.3.2.2 Electrocyclic Reactions

When both lines are drawn into the same lobe it is suprafacial, and
when there is one line dawn into the top lobe and one into the bottom,
it is antarafacial. Since this is neither a p nor a orbital, it is given the
Greek letter w.
6.3.2.3 Sigmatropic Rearrangement
6.3.2.4 Group Transfer Reactions
Report No8 (7/15)

1. Explain the following rearrangement.