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PERICYCLIC REACTIONS
peri =around, cyclic = circle or ring
Polar react. (nucleophiles and electrophiles) Nu E
Energy Energy
inter-
starting product starting mediate inter-
material material mediate product
5
2) Cycloaddition reactions:- Two linear conjugated polyenes
converted onto a cyclic product in one step. Again, the
stereochemistry of the reaction is remarkably reproducible. e.g.
3) Sigmatropic rearrangement reactions:-These involve a
concerted migration of atoms or of groups of atoms. E.g.
migration of a s-bond. The numbering refers to the number of
atoms in the transition state on either side of where bonds are
made or broken.
Frontier Molecular Orbitals
nodes
Nodal Plane
ANTI-BONDING
MOLECULAR
ORBITAL
E
N
*
E
s ATOMIC ORBITAL
R
G
+
Y
BONDING
MOLECULAR
ORBITAL
-Bond
One s Atomic Orbital and One sp3 Atomic Orbital
Molecular Orbitals
ANTI-BONDING
MOLECULAR
ORBITAL
E
N *
E
R
sp3 ATOMIC ORBITAL
G
Y
+
BONDING
MOLECULAR
ORBITAL
-Bond:
Two p Atomic Orbitals Molecular Orbitals
Nodal Plane
ANTI-BONDING
MOLECULAR
ORBITAL
E *
N
E p-atomic orbitals
R +
G
Y
BONDING
MOLECULAR
ORBITAL
The linear combination of
n atomic orbitals
n molecular orbitals
A Molecular Orbital Description of Ethane
Asymmetric
(LUMO)
(HOMO)
Symmetric
Four p atomic orbitals interact to give the four p MOs of
1,3-butadiene
(LUMO)
Asymmetric
Symmetric (LUMO)(HOMO)
(HOMO)
Asymmetric
Symmetric
NOTE
A MO is bonding if the number of bonding interactions is
greater than the number of nodes
Asymmetric
(LUMO)
Symmetric
(LUMO) (HOMO)
Asymmetric
(HOMO)
Symmetric
Asymmetric
Symmetric
The Allyl Cation, Radical and Anion 3p AOs to give 3 MOs
Cl Cl H
Polar
Solvent
B
Cl Cl BH
Allyl Cation Allyl Radical Allyl Anion
Thus, allyl systems result from the combination of 3 conjugated p-
orbitals. Therefore, this will result in 3 -molecular orbitals.
3 LUMO LUMO
2 nodes
1 0 nodes HOMO
- molecular boning of Pentadiene
Pentenyl Pentenyl Pentenyl
O
cation (4e) radical (5e) anion (6e)
Pentenyl
cation (4e)
Mirror Plane C2 axis
5 5 4 nodes
4 nodes S A
4 4 3 nodes
3 nodes A
LUMO S
LUMO
3 3 2 nodes
2 nodes LUMO
LUMO S
HOMO A
HOMO
2 2 1 node
1 node HOMO
HOMO
A S
1 0 nodes S A
1 0 nodes
These are pericyclic processes that involves the cyclization of a
conjugated polyene. The electrocyclic reactions are intramolecular
reactions.
Thermal condition
Thermal condition
h
Photochemichal condition
Rules for Electrocyclic Reactions
Frontier Molecular Orbital Method
Q5
Q6
Q 9
CYCLOADDITION REACTIONS
Cycloaddition reactions are intermolecular pericyclic processes involving
the formation of a ring from two independent conjugated systems through
the formation of two new -bonds at the termini of the -systems. The
reverse process is called cycloreversion or is referred to as a retro-reaction.
Suprafacial HOMO 2
0%
165C
78%
900 atm
17 hours
Rules for Cylcoadditions - Suprafacial
Cycloadditions
58
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)
59
Frontier Orbital Analysis of a [4 + 2]
Cycloaddition Reaction
A [2 + 2] Cycloaddition Reaction
Frontier Orbital Analysis of a [4 + 2]
Cycloaddition Reaction
Frontier MO Analysis of the
[2 + 2] Cycloaddition Reaction
Diels-Alder Cycloaddition Reaction:
6 -Electron Transition State
Suprafacial 2 HOMO
4s + 2s
Suprafacial 2 LUMO
Diels-Alder Reaction Transition State Geometry
Suprafacial
Diene HOMO 2
EWG EWG
EWG EWG EWG EWG
MESO
Dieneophile LUMO 2
Suprafacial
4s + 2s
Suprafacial
One of two equally
likely transition states
Diene HOMO 2 See Next 2 Slides
EWG
EWG EWG EWG
EWG
EWG
EWG EWG
Dieneophile LUMO 2
Suprafacial
i.e. enantiomers
4s + 2s
Regiochemistry Issues in the Diels-Alder
Reaction
C/Z/X C/Z/X
C/Z/X C/Z/X
X X
Except
X X
C = Extending Conjugation
C/Z/X C/Z/X
X X
X X
Except
C = Extending Conjugation
O O O Endo O
O
Exo
O
O O O O
O
EWG
HOMO-alkene
HOMO-alkene
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
84
Sigmatropic Rearrangements
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
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
ANTARA
SUPRA Based on McMurry, Organic Chemistry,
89
Chapter 30, 6th edition, (c) 2003
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
Suprafacial H
5 5
1 1 4 H
H 4 H
-bond to
be broken 1 3 1 3
2 2
4n + 2 Suprafacial Antarafacial
h
Suprafacial H
H H
Antarafacial
2.