Three Classes of Organic Reactions

Polar reactions
O OH OH H
+

OH OH OH OH O H OH O

OH2

..

..

OH

O O

H O O

Radical reactions

CH3CH2 +

Cl

Cl

CH3CH2Cl + Cl

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

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 H H3C H

Certain common features of pericyclic reactions

They are all concerted reactions Therefore, there is one 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

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 -system
B B

disrotatory ring closure

disrotatory
B A A B

-system

-system
B A

conrotatory ring closure

conrotatory
B A A B

CO2Me CO2Me Conrotatory H CO2Me H CO2Me

example:
H

Selection rules for electrocyclic reactions

n 4q Thermally allowed, Thermally forbidden, photochemically forbidden photochemically allowed

Conrotatory Disrotatory

Disrotatory Conrotatory

4q+2

q = integer

Q. Have the following reactions proceeded in the conrotatory or disrotatory manner? Should they proceed under thermal or photochemical influence?

*
H H

CH3

CH3 H H CH3

*
CH3

H H CH3

CH3 H

H H3C H

H3C H

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

Sigmatropic reactions
These reactions are defined as involving migration of a bond that is flanked by one or more conjugated systems to a new position within the system
etc

migrating bond
etc

The reaction is termed [ i, j ] sigmatropic shift when the bond migrates from position [1,1] to position [i,j]. Examples:
1 2 3 3 2 1 2 3

[3,3] sigmatropic shift

1 1 2 3

2 1 3 3 2 1

2 3 1 2

[1,3] sigmatropic shift

3

Q. Classify the following sigmatropic reactions of order [i,j]

H H H H H D D H D2C H H H

H3C

[1,5]

[2,3]
S R2 R1 R2

*
R1

CH3

CH3

[1,5]

A Cope rearrangement
C6H5 C6H5

CH3

CH3

A Claisen rearrangement
O CH3 CH3 O

Q. Give the product of the following reaction.

O

O [3,3]

OH

Q.

Suggest a mechanism
O H3C CH3 H3C OH CH3

O O H3C CH3 H3C CH3

H O H3C CH3

A biological reaction involving an electrocyclic reaction and a sigmatropic reaction

H3C CH3

H3C
CH3 CH3

CH3 CH3

CH3

CH3 H HO H

an electrocyclic reaction h
HO

CH3 H

provitamin D3

7-dehydro cholesterol

H3C CH3

CH3 CH3

CH2

[1,7] sigmatropic shift

H HO

vitamin D3

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 CH3

H3C

CH3

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

O O O O

heat
O O

UV light

a [2+2] cycloaddition reaction

Q. Classify the following as [m+n] cycloaddition reactions

CH3 CH3 O O

CH2

OCH3 +

OCH3

*
CH2

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 H O NH3 + O O NH H O

O Cl S CCl3

CCl3

Captan (agricultural fungicide)

The endo rule for Diels-Alder reaction

O H O

O
O O

H H O O O
H H

'exo' adduct (not formed)

'endo' adduct (formed)

H + H

'endo' adduct

Why pericyclic?
Because all first-order bonding changes occur on a closed curve.

Conrotatory cyclisation of butadiene