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Pericyclic Reaction Theory


I. Definitions
A. Cycloaddition
B. Electrocyclic reaction
C. Sigmatropic reaction
II. Conservation of Orbital Symmetry
A. Symmetry correlation diagrams
B. Frontier orbital approach
C. Generalized Woodward-Hoffmann selection rules
III. Transition State Aromaticity
A. Hckel and Mbius aromaticity
B. Interaction diagrams
C. Aromatic and antiaromatic transition states
IV. Summary
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A
hv
hv
A
Ph
Ph
+
Ph
Ph
CO
2
CH
3
CO
2
CH
3
+
CO
2
CH
3
CO
2
CH
3
hv
A
OAc
H
H
D
A
OAc H
H
D
thermally forbidden
photochemically allowed
photochemically forbidden
thermally allowed
inversion of configuration
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I. Definitions
A. Cycloaddition
Pericyclic reaction: one in which concerted bond breaking and bond
formation occur through a reorganization of electrons within a closed loop
of interacting orbitals.
Ring formation by transfer of electrons from t bonds to new o bonds.
Cycloreversion: reverse process.
+
t2 + t2
o2 + o2
t4 + t2
o2 + o2
+
t4 + t4
+
t2 + t2
t2 + o2 + o2
t2 + t2
+ o2 + o2
2 + 2 cycloaddition/cycloreversion
4+2
4+4
2+2
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I. Definitions
A. Cycloaddition
or or
suprafacial (s)
process
antarafacial (a)
process
t4s + t2s
(t2s + t2s + t2s)
(t2a + t2a + t2s)
t4a + t2s
(t2s + t2a + t2s)
(t2a + t2s + t2s)
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I. Definitions
B. Electrocyclic reaction
Formation of a single bond between the termini of a linear t system,
and the reverse process.
electrocyclic ring closure
electrocyclic ring opening
conrotatory process
disrotatory process
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I. Definitions
B. Electrocyclic reaction
disrotatory
conrotatory
t6s
(t2s + t2s + t2s)
t4s + o2s
(t2s + t2s + o2s)
t6a
(t2s + t2s + t2a)
t4s + o2a
(t2s + t2s + o2a)
t4a + o2s
(t2s + t2a + o2s)
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I. Definitions
C. Sigmatropic reaction
Bond migration over a t system.
R R
1
2
3
1'
1'
3
2
1
1
2
3
1'
2'
3'
3
3'
[1,3] sigmatropic shift
[3,3] sigmatropic shift
(Cope rearrangement)
[1,3]
retention
a
c
b
a
c
b
t2s + o2s
supra migration
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I. Definitions
C. Sigmatropic reaction
a
c
b
a
c
b
[1,5]
inversion
[1,5]
retention
a
c
b
a
c
b
[3,3]
t4s + o2a
(t2s + t2s + o2a)
supra migration
t4a + o2s
(t2a + t2s + o2s)
antara migration
t2s + t2s + o2s
supra/supra migration
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II. Conservation of Orbital Symmetry
A. Symmetry correlation diagrams
1. cycloaddition/cycloreversion
Woodward-Hoffmann Rules
In any concerted process, the starting material orbitals must be
transformed into product orbitals of the same symmetry.
(There are other symmetry elements as well, but no additional information
is gained; o
1
and o
2
are sufficient to differentiate orbital symmetries.)
o
1
o
2
o
1
o
2
+
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II. Conservation of Orbital Symmetry
A. Symmetry correlation diagrams
1. cycloaddition/cycloreversion
o
1
o
2
mix t
orbitals
+
o
1
o
2
o
1
o
2
o
1
o
2
mix o
orbitals
o
2
o
1
o
1
o
2
+
not symmetry correct
with respect to o
1

not symmetry correct
with respect to o
2

t
1
- t
2

= t
SS

o
1
o
2
t
1
+ t
2

= t
AS

o
1
+ o
2

= o
SS

o
1
- o
2

= o
SA

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II. Conservation of Orbital Symmetry
A. Symmetry correlation diagrams
1. cycloaddition/cycloreversion
Orbital correlation diagram:
t*
AA
t*
SA
t
AS
t
SS
o*
AA
o*
AS
o
SA
o
SS
thermally (black):
g.s. upper e.s.
symmetry forbidden

photochemically (blue):
1
st
e.s. 1
st
e.s.
symmetry allowed
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II. Conservation of Orbital Symmetry
A. Symmetry correlation diagrams
1. cycloaddition/cycloreversion
+
o
o plane is only symmetry element
t orbitals are correct, need to mix os
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II. Conservation of Orbital Symmetry
A. Symmetry correlation diagrams
1. cycloaddition/cycloreversion

4
A
t
2
A

3
S

2
A
t
1
S

1
S
o
4
A
o
3
S
t
2
A
t
1
S
o
2
A
o
1
S
thermally
allowed,
photochemically
forbidden
avoided crossings
-orbitals of the same symmetry do not cross
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II. Conservation of Orbital Symmetry
A. Symmetry correlation diagrams
1. cycloaddition/cycloreversion
General for all-supra cycloadditions/cycloreversions:

allowed forbidden
A 4n+2 4n
hv 4n 4n+2
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II. Conservation of Orbital Symmetry
A. Symmetry correlation diagrams
2. electrocyclic reactions
conrotatory
disrotatory
c
2
axis
o plane
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II. Conservation of Orbital Symmetry
A. Symmetry correlation diagrams
2. electrocyclic reactions
S
A
S
A
A
S
A
S
A
S
A
S
A
A
S
S
conrotatory (c
2
)
A allowed
hv forbidden
disrotatory (o)
A forbidden
hv allowed
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II. Conservation of Orbital Symmetry
A. Symmetry correlation diagrams
2. electrocyclic reactions
General for electrocyclic reactions:

A allowed hv allowed
conrotatory 4n 4n+2
disrotatory 4n+2 4n

4n conrotatory disrotatory
4n+2 disrotatory conrotatory
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II. Conservation of Orbital Symmetry
B. Frontier orbital approach: sigmatropic reactions
[1,3]-H:
suprafacial



antarafacial
No symmetry elements; symmetry correlation diagrams not relevant.

Look at orbital symmetry conservation in HOMO/LUMO:
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II. Conservation of Orbital Symmetry
B. Frontier orbital approach: sigmatropic reactions
mix
LUMO


HOMO
isolated
orbitals
A forbidden
hv allowed
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II. Conservation of Orbital Symmetry
B. Frontier orbital approach: sigmatropic reactions
General for sigmatropic reactions:

A allowed hv allowed
[1,3]-H (4n) antara supra
[1,5]-H (4n+2) supra antara

[i,j]-alkyl:
4n supra inversion retention
antara retention inversion
4n+2 supra retention inversion
antara inversion retention
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II. Conservation of Orbital Symmetry
C. Generalized Woodward-Hoffmann pericyclic selection rules
A pericyclic reaction is thermally allowed if the total number of
(4n+2) s and (4n) a components is odd.
or - If broken down into two electron components, a pericyclic reaction
is thermally allowed if the number of 2s components is odd.
+
+
H H
H
2s + 2s hv allowed

2s + 2s + 2s A allowed

2s + 2s hv

2s + 2a A

2s + 2s hv
2s + 2a A
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III. Transition State Aromaticity
A. Hckel and Mbius aromaticity
Dewar-Zimmerman Selection Rules
Hckel:





Mbius:
4n+2 e

= aromatic
4n e

= antiaromatic
4n e

= aromatic
4n+2 e

= antiaromatic
phase
inversion
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III. Transition State Aromaticity
B. Interaction diagrams
Fundamental topology of interacting orbitals:








omit skeletal framework
disregard spatial orientations of orbitals
use p orbitals to represent all orbitals
assign algebraic signs to the orbitals to minimize the number of
phase inversions
= =
= =
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III. Transition State Aromaticity
B. Interaction diagrams
=
=
Even number of phase
inversions can always
be reduced to zero.
Odd number of phase
inversions can always
be reduced to one.
No phase inversions = Hckel interaction
One phase inversion = Mbius interaction
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III. Transition State Aromaticity
C. Aromatic and antiaromatic transition states
Examine topology of interacting orbitals in TS:
Hckel Mbius
4n antiaromatic aromatic
4n+2 aromatic antiaromatic
Aromatic TS A allowed (hv forbidden)
Antiaromatic TS A forbidden (hv allowed)
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III. Transition State Aromaticity
C. Aromatic and antiaromatic transition states

no phase inversions
6 e

Hckel TS
aromatic
A allowed
= =
no phase inversions
4 e

Hckel TS
antiaromatic
A forbidden
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III. Transition State Aromaticity
C. Aromatic and antiaromatic transition states
=
=
disrot:
conrot:
4 e

Hckel
A forbidden


4 e

Mbius
A allowed
R R
=
4 e

Mbius
A allowed
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IV. Summary
O
O
+
10 e

supra/supra cycloaddition
2s + 2s + 2s + 2s + 2s
10 e

Hckel TS
A allowed
CH
3
H
H
H
3
C
H
H
=
4 e

supra/antara cycloreversion
2s + 2a
4 e

Mbius TS
A allowed
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IV. Summary
=
6 e

antara/antara cycloaddition
2s + 2a + 2a
6 e

Hckel TS
A allowed
Ph
Ph
O
O O
O
O
O
Ph
Ph
A
Ph
Ph
4 e

conrotatory
electrocyclic ring opening
2s + 2a
4 e

Mbius TS
6 e

supra/supra cycloaddition
2s + 2s + 2s
6 e

Hckel TS