Pericyclic

reactions
Presenter
Harmanpreet Kaur
M.Sc. (II) Sem
Chemistry
D.A.V College
 Pericyclic Reactions

•Polar react. (nucleophiles and electrophiles) N

u
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

LUM O: Low est uoccupied M O

HO M O: Highest occupied M O
Molecular orbitals
1,3-butadiene
HOM O

L U M O  -b o n d

H O M O  -b o n d

C o n ro ta to ry
B o th ro ta te s a m e w a y

Stereospesific react.

H 3C CH3 H H
H H
CH3 CH3

E ,E C is

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

E ,Z T ra n s
Molecular orbitals HOMO
hexatriene
LUMO-bond LUMO-bond

Disrotatory HOMO-bond
Rotationoppositeway

H 3C C H 3
C H 3 C H 3
E E
C is

H 3 C C H 3
H 3 C
C H 3
E Z
T ra n s

Symmetry allowed react

No. of electrons Reactions in the ground state

4n Conrotatory

4n + 2 Disrotatory
Photochemical electrocyclic react.

h

H O M O e x ite t s ta te
(= L U M O g ro u n d s ta te )

D is r o ta to ry

N o . o f e le c tr o n s R e a c tio n s in th e g r o u n d s ta te R e a c tio n s in e x ite d s ta te

(te r m a l) (P h o to c h e m .)
4 n C o n ro ta to ry D is r o ta to r y

4 n + 2 D is r o ta to r y C o n ro ta to ry
 Cycloadditions (i.e. Diels Alder)

S u p r a fa c ia l c y c lo a d d .

L U M O - d ie n e
H O M O - D ie n e
[
4
+2
]

L U M O - d ie n o p h ile H O M O - d ie n o p h ile

[
4
+2]
A
C
AC
BD
BD

Stereospesific react.
 endo - exo selectivity
O

O O O Endo O
E
x
o
O O
O OOO
O

H O M O - D ie n e H
OMO
-Di
e n
e

P
r
i
mar
yi
nt
er
a
ct
.
,b
on
d
f
or
ma
t
io
n

S
e
c
on
d
ar
yi
nt
er
a
ct
.
,e
xt
r
aT#
S
s
ta
bi
l
.
O O O L
UMO
-di
e n
oph
il
e
O O O

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

Ethene etc, very low react.

Michael accept. L U M O -a lk e n e
L U M O -a lk e n e
Lower LUMO
E W G
H O M O - L U M O g a p

E W G
H O M O -a lk e n e

H O M O -a lk e n e
[2+2] Cycloadditions
S u p r a fa c ia l c y c lo a d d . Antarafacial cycloadd. (termal cond.) S
upra
fac
ialc
yclo
add
.(p
hoto
che
m .c
ond
.)

HOMO-alkene
H O M O - D ie n e HOM O-alke
ne
e
xite
ds tate
h
LUMO -alkene

L U M O -a lk e n e L
U M
O -a
lke
ne

Geometrical constrains
Difficult to make small rings
by antrafacial cycloadd

N o . o f e le c tr o n s R e a c tio n s in th e g r o u n d s ta te R e a c tio n s in e x ite d s ta te

(te r m a l) (P h o to c h e m .)
4 n A n ta r a fa c ia l S u p r a fa c ia l

4 n + 2 S u p r a fa c ia l A n ta r a fa c ia l
 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

E m pty p-orb
LU M O of carbene
R R H O M O o f c a rb e n e

C C

R R

H O M O alkene
L U M O a lk e n e
 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

C
o
p
er
e
ar
ra
n
ge
me
n
t

2 12
1 3 3

R R
13
13 2
2

O
x
y-
Cop
er
ea
rr
an
ge
me
nt

2 12 2
1 1
3 3 t
aut 3

H
O H
O13 O
13 S u p r a fa c ia l
13 2
2 2
[1,5] Rearrangement (H-shift)

S
u
pr
af
aci
al H
5 5
1 1 4 H
H 4 H
-bondto
bebroken 1 3 1 3
2 2

N o . o f e le c tr o n s R e a c tio n s in th e g r o u n d s ta te R e a c tio n s in e x ite d s ta te

(te r m a l) (P h o to c h e m .)
4 n A n ta r a fa c ia l S u p r a fa c ia l

4 n + 2 S u p r a fa c ia l A n ta r a fa c ia l

[1,3] Rearrangement (H-shift)

h 
S u p r a fa c ia l H
H H

A n ta r a fa c ia l

T o o s tr a in e d T S #