Analysis of

Pericyclic Reactions
and Hydrogen Shift
Prepared by
Muhammad Faizan (BX500156)
And
Fakhar Abbas (BX500152)
 Pericyclic Reactions

•Polar react. (nucleophiles and electrophiles) Nu E

•Radical react. R R'

•Pericyclic react. (concerted, cyclic TS#)

•Electrocyclic react. •Rearrangement of polyene

•Termal (react. in ground state)
•Cycloadditions (i.e. Diels Alder)
or photochemical
•Sigmatropic rearrangement
(react of exited state)
Symmetry Allowed React.

Woodward Hoffmann rules

Symmetry in reactants are preserved during pericyclic react.

Results can generally be predicted just by looking at Front Orbitals

(FMO; HOMO and LUMO) - Fukui

LUMO: Lowest uoccupied MO

HOMO: Highest occupied MO

Molecular orbitals
1,3-butadiene
HOMO

LUMO -bond

HOMO -bond

Conrotatory
Both rotate same way

Stereospesific react.

H3C CH3 H H
H H
CH3 CH3

E,E Cis

S: Symmetric
A: Antisym. H3C H H CH3
H H 3C
CH3 H

E,Z Trans
Molecular orbitals HOMO
hexatriene
LUMO -bond LUMO -bond

Disrotatory HOMO -bond

Rotation opposite way

H3C CH3
CH3 CH3
E E
Cis

H3 C CH3

H3C
CH3
E Z
Trans

Symmetry allowed react

No. of electrons Reactions in the ground state

4n Conrotatory

4n + 2 Disrotatory
Photochemical electrocyclic react.

h

HOMO exitet state

(= LUMO ground state)

Disrotatory

No. of electrons Reactions in the ground state Reactions in exited state

(termal) (Photochem.)
4n Conrotatory Disrotatory

4n + 2 Disrotatory Conrotatory
 Cycloadditions (i.e. Diels Alder)
Suprafacial cycloadd.

LUMO - diene
HOMO - Diene
[4+2]

LUMO - dienophile HOMO - dienophile

[4+2]
A C
A C
B D
B D

Stereospesific react.
 endo - exo selectivity
O

O O O Endo O
Exo
O O
O O O O
O

HOMO - Diene HOMO - Diene

Primary interact., bond formation

Secondary interact., extra TS# stabil.

O O O LUMO - dienophile
O O O

Normal electron demand DA - Electron poor dienophile (Michael accept.)

Ethene etc, very low react.

Michael accept. LUMO -alkene
LUMO -alkene
Lower LUMO
EWG
HOMO - LUMO gap

EWG
HOMO-alkene

HOMO-alkene
[2+2] Cycloadditions
Suprafacial cycloadd. Antarafacial cycloadd. (termal cond.)
Suprafacial cycloadd. (photochem. cond.)

HOMO-alkene
HOMO - Diene HOMO-alkene
exited state
h
LUMO -alkene

LUMO -alkene LUMO -alkene

Geometrical constrains
Difficult to make small rings
by antrafacial cycloadd

No. of electrons Reactions in the ground state Reactions in exited state

(termal) (Photochem.)
4n Antarafacial Suprafacial

4n + 2 Suprafacial Antarafacial
 Carbene Cycloadditions
Singlet Carbene

Empty p-orb
LUMO of carbene
R R
R

C
R R
sp2 hybr orbital with lone pair
R
HOMO of carbene

Empty p-orb
LUMO of carbene
R R HOMO of carbene

C C

R R

HOMO alkene
LUMO alkene
 Sigmatropic Rearrangements
[3,3] Rearrangements; Claisen rearrang. etc.

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 3
HO 1 3 O 1 3 Suprafacial
2 2 2
[1,5] Rearrangement (H-shift)

Suprafacial H
5 5
1 1 4 H
H 4 H
-bond to
be broken 1 3 1 3
2 2

No. of electrons Reactions in the ground state Reactions in exited state

(termal) (Photochem.)
4n Antarafacial Suprafacial

4n + 2 Suprafacial Antarafacial

[1,3] Rearrangement (H-shift)

h
Suprafacial H
H H
H

Antarafacial

Too strained TS#

Thank you…