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Pericyclic Reaction

Three Classes of Organic Reactions


Polar reactions
Y

R = aliphatic as well as aromatic


O

OH
+

OH

..

..

OH

O
H

OH

O
O

OH2

OH

OH

OH

H
O

Radical reactions

CH3CH2 +

Cl

Cl

CH3CH2Cl + Cl

Pericyclic reactions
This reaction occurs as a result of a cyclic reorganization of electrons

OH

Three most common types of pericyclic reactions


Elcetrocyclic reactions
new bond

Cycloaddition reactions
new bond
+

new bond

Sigmatropic reactions
H3C

H3C

new bond is formed


bond is broken in the
middle of the system

CH2
H3C

H3C

Certain common features of pericyclic reactions


They are all concerted reactions
Therefore, there is one transition state (TS) and no intermediates

As the reactions are concerted, they are highly stereoselective

The reactions are generally not effected by catalysts


or by a change in solvent or reagent polarity

Most of the reactions are reversible


Generally undergo by TS

Only way to influenced them are by thermally or photochemically

Pericyclic: The reactions that proceed via cyclic TS

Usually pericyclic reactions are induced thermally and/or photochemically

Electrocyclic reaction
Me

Me

Me

Me

Me

Me

Me

Me

Me
Me

Me
Me

What determine the geometry of the cyclized product?

Electrocyclic Reactions
These reactions are defined as involving the cyclization of an n pi-electron
system to an (n-2)pi + 2sigma-electron system or the reverse process.
(n-2)e

(n-2)e

The reactions are reversible.


Observance of ring opening and ring closure depends
upon the thermodynamic stability of the open and closed forms.

Two distinct modes are possible.


-system

disrotatory
ring closure

-system

disrotatory
B

-system

-system

conrotatory

conrotatory
ring closure

CO2Me
CO2Me
Conrotatory
H
CO2Me

example:

H
CO2Me

H
H

Elcetrocyclic reactions
CH3

CH3
CH3

tion
a
t
o
r
con

H
CH3
H

CH3

disrota
tion

H
CH3
HH
CH3
CH3
H

rota
n
o
c

tion

H
H
CH3

CH3
CH3

disrota
tion

H
CH3
H

F bond length

1.42 A0

H bond length

0.74 A0

F bond strength

38 Kcal/mol

H bond strength

104 Kcal/mol

Overlap of in-phase p orbitals gives a bonding molecular orbital that is lower in energy
than the p atomic orbitals. Overlap of out-of-phase p atomic orbitals gives an antibonding
molecular orbital that is higher in energy than the p atomic orbitals.

Four p atomic orbitals overlap to give the four molecular orbitals


of 1,3-butadiene

HOMO

HOMO

Selection rules for electrocyclic reactions


No. pielectrons

Thermally allowed,
Thermally forbidden,
photochemically forbidden photochemically allowed

4q

Conrotatory

Disrotatory

4q+2

Disrotatory

Conrotatory

q = integer

CH3 disro
H H
CH3

on
tati

h
conrot
ation

CH3

CH3
CH3

CH3

CH3
H
CH3
H

tion
a
t
o
disr

CH3

CH3

con
rot
atio
n

CH3

CH3

Six p atomic orbitals overlap to give the six molecular orbitals


of 1,3,5-hexatriene

HOMO

LUMO

Q. Have the following reactions proceeded in the conrotatory or disrotatory


manner? Should they proceed under thermal or photochemical influence?

*
H

CH3

CH3
H
H

H
H

CH3

CH3

Q. Show that the cyclobutane below open by two alternative conrotarory procsses.
What is the product in each instance? Do you expect them to be formed in equal
amounts?
CH3
H
H
CH3

A biological reaction involving an electrocyclic reaction and a sigmatropic reaction


H3C

H3C
CH3

CH3

CH3

CH3

CH3

an electrocyclic reaction

CH3

CH3

CH3

h
HO

HO

provitamin D3

7-dehydro cholesterol

H3C
CH3

CH2

[1,7] sigmatropic shift


H
HO

vitamin D3

CH3
CH3

7-dehydrocholesterol, a steriod formed in skin, is converted into


Vitamin D3 by two pericyclic reactions
Deficiency in vitamin D causes rickets.
Deficiency in vitamin D can be prevented by getting
enough sun.
Too much vitamin D is harmful- skin pigmentation
protects the skin from the suns UV rays.

Cycloaddition reactions

H3C

H3C

CH3

O
O
O

CH3

a [4+2]
cycloaddition reaction
(Diels-Alder reaction)

heat
O

UV light

a [2+2]
cycloaddition reaction

General description of Diels-Alder reaction


CHO

CHO

diene

dienophile

adduct

+
NO2

diene

dienophile

NO2

adduct

Dienes permanently in s-cis conformation (Diels-Alder reactions are excellent)


O

Dienes permanently in s-trans conformation (cannot undergo Diels-Alder reaction)

Captan
(an industrial application of Diels-Alder reaction)
O

NH3

O
Cl

NH

CCl3
S

Captan
(agricultural fungicide)

CCl3

The endo rule for Diels-Alder reaction


O

O
O

H
O

'exo' adduct (not formed)

'endo' adduct (formed)


H
+

'endo' adduct

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