1mam Material

Engineering Chemistry III Prof. S. Sankararaman

Indian Institute of Technology Madras

1

Pericyclic Reactions

Definition:

1. Concerted reaction that proceed via a cyclic transition state

2. No distinct intermediates in the reaction

3. Bond forming and bond breaking steps are simultaneous but not necessarily

synchronous

Classification:

1. Electrocyclic ring closing and ring opening reaction

2. Cycloaddition and Cycloreversion reaction

3. Sigmatropic Rearrangements

4. Chelotropic Reaction

5. Group transfer Reaction

Methods of Analyzing Pericyclic Reaction

1. Orbital symmetry correlation method (Woodward, Hoffmann, Longuet-Higgins and Abrahamson)

2. The frontier orbital method (Woodward, Hoffmann and Fukui)

3. Transition state aromaticity method (Dewar and Zimmerman)

Woodward-Hoffmann Rules: Predicts the allowedness or otherwise of pericyclic reactions

under thermal and photochemical conditions using the above methods. Therefore a basic

understanding of molecular orbitals of conjugated polyene systems and their symmetry

properties is essential to apply the above methods.



2

Constructing MO diagram of polyene systems:

1. Although there are C-C and C-H sigma bonds present in the molecule, the MOs

can be constructed independently of them. Although there may be a change in the

hybridization of carbon atoms during the course of a pericyclic reaction, the MO

levels of the sigma framework are relatively unaffected.

2. For a conjugated polyene system containing n (n = even) electrons, there will be

n/2 bonding molecular orbitals that are filled MOs and n/2 antibonding MOs that

are empty in the ground state electronic configuration of the molecule.

3. The lowest energy MO has zero nodes, the next higher one has one node and the

second higher has two nodes and so on.

The nth MO will have (n-1) nodes.

4. The nodal points are found at the most symmetric points in a MO.

In other words, no MO can be symmetric as well as antisymmetric at the same time

with respect to any existing molecular symmetry element. For example the 2 MO

of butadiene has a node at the center of the bond connecting C2 and C3. It is

incorrect to assign this node to the center of the bond connecting C1 and C2.

node node

2 Correct 2

Incorrect



3

1

3

*

ethylene ethylene butadiene

4

Formation of MOs of butadiene from MOs of ethylene

4



4

1

2

3

4

1

2

3

4

5

6

antibonding

bonding

MOs of ethylene Butadiene and hexatriene



5

Frontier orbital method:

Highest occupied MO (HOMO) filled

Lowest unoccupied MO (LUMO) empty

Analysis based on the interaction of HOMO of one Component and LUMO of the other

component.

If HOMO-LUMO interaction leads to bonding then the reaction is allowed. If not it is

forbidden.

HOMO-LUMO gap is important. The closer it is the faster the reaction.

ELECTROCYCLIC REACTIONS

1. Cyclization of an acyclic conjugated polyene system

2. The terminal carbons interact to form a sigma bond

3. Cyclic transition state involving either 4n electrons or 4n+2 electrons.

Electrocyclization of butadiene (4n) and hexatriene (4n+2)

(1)

(2)



6

Modes of ring closing/ring opening reactions - Stereochemistry

CH3H3C

H HH

CH3CH3

H

CH3H

H3C H

conrotatory disrotatory

HH3C

H CH3

HCH3

HH3C

HH

H3C CH3


CH3H

H3C HH3C

HCH3

H

HH

H3C CH3


Z, E

Z, Z

E, E

cis

trans

cis

cis

trans

trans

(3)

(4)

(5)



7

Frontier orbital method for electrocyclic reactions

antibonding interaction in the TS

bonding interactionin the TS

conrotation

bonding orbital

disrotation

antibonding orbital2 HOMO of butadiene

2 HOMO of butadiene

disrotation


bonding orbital

conrotation

antibonding orbitalantibonding interactionin the TS3 HOMO of hexatriene

3 HOMO of hexatriene



8

antibonding interaction in the TS


disrotation

bonding orbital

conrotation

antibonding orbital

conrotation


bonding orbital

disrotation

antibonding interactionin the TS

antibonding orbital

HOMO of excitedstate butadiene

HOMO of excitedstate hexatriene

HOMO of excitedstate butadiene

HOMO of excitedstate hexatriene



9

Woodward Hoffmann rules for electrocyclic reactions

Four-membered Ring Systems:

The synthesis of cyclobutene was first reported by Willsttter. The thermal ring opening of

cyclobutene occurs readily at 150 oC to give 1,3-butadiene.

150 oC

Thermal isomerization of cyclobutene to 1,3-butadiene

The stereochemistry of the ring opening has been studied systematically in detail by

Vogel and Criegee even before the theory of pericyclic reactions and Woodward-

Hoffmann rules were developed. The electrocyclic ring opening of 3,4-disubstitued

cyclobutenes yield products arising from the conrotatory mode of ring opening with high

stereospecificity as illusrated below.

Allowedness of the reaction System (no of electrons)

Mode of reaction Thermal Photochemical

4n conrotatory allowed forbidden

4n disrotatory forbidden allowed

4n+2 conrotatory forbidden allowed

4n+2 disrotatory allowed forbidden



10

HMe

MeHMe

MeMeH

Me

Me

H

Me

150 oC

HMe

HMeMe

MeHH

Me

Me

Me

Me

150 oC

MeCOOMe

COOMeMePh

PhMeCOOMe

Ph

Ph

COOMe

Me

70 oC

MeMe

Me

Me

H

H

only E, Z isomer

only Z, Z isomer E, E isomernot formed

Stereochemistry of thermal electrocyclic ring opening of cyclobutenes.

Thermal isomerization of the highly substituted dienes shown below takes place through

the formation of the cyclobutene intermediate by a conrotatory pathway. None of the

symmetry disallowed disrotatory products were formed even after 51 days at +124 oC

which allowed the estimation of a lower limit of 7.3 kcal/mole of energy difference

between the conrotatory and disrotatory modes of reaction.

NoelText Boxhere the carbon is sp2 hybridised so bond angle is 120 so the bonds point either inside or outsidecis => con =>point in same directiontrans => con =>point in opp directioncis => dis=>point in opp directiontrans => dis =>point in same direction

NoelText Boxcis

NoelText Boxboth H point up and both Me point down

NoelText Boxtrans

NoelText Boxcon

NoelText Boxcon

NoelCalloutone H points up and other points down

NoelText Boxcis

NoelText Boxcon

NoelText Boxboth Me point up and both Me point down



11

Stereoselective thermal isomerization of 1,3-butadiene derivatives.

CD3Ph

CH3

PhPh

Ph Ph

Ph

PhPh

CH3

CD3PhCH3

Ph

CD3Ph

Ph

PhPh

CH3

CD3Ph

Ph

CD3CH3

Ph

PhPh

Phor

51 days at 140o C The photochemical ring closing of butadiene and E,E and Z,E-hexa-2,4-diene has been

studied by Srinivasan and the reaction follows the disroatory mode as predicted by the

Woodward-Hoffmann rules.

h253 nm

h

h

Photochemical electrocyclization of 1,3-butadiene derivatives.

Benzocyclobutene is another well studied 4 electron system and the electrocyclic ring

opening gives a very reactive intermediate, namely ortho quinodimethane.

NoelText Boxopp dir

NoelText Boxsame dir

NoelText Boxdis

NoelText Boxdis

NoelText Boxcis

NoelText Boxtrans


NoelText Boxcon

NoelText Boxcis



12

Thermal isomerization of benzocyclobutene to ortho quinodimethane.

Stereoselective thermal isomerization of benzocyclobutene derivatives

Ph

Ph

Ph

Ph

rt TCNECN

CNCN

CN

Ph

H Ph

H

quantitative

Ph

PhPh

rt TCNECN

CNCN

CN

Ph

Ph H

H

quantitative

Ph

con

con

meso

racemic

CH2Cl2

CH2Cl2

Examples of thermal and photochemical electrocyclic reaction of cyclohexadiene-

hexatriene system are abundant in the literature.] According to the Woodward-Hoffmann

rules this six electron system is predicted to undergo disrotatory cyclization under

thermal and conrotatory ring closure under photochemical conditions. Isomeric

octatrienes conform to the above predictions and undergo stereospecific

electrocyclization as shown below.

Stereospecific electrocyclic ring closure of isomeric hexa-1,3-5-trienes.

HH

Me

Me

150 oC Me

Medis

HMe

H

Me

150 oC Me

Medis

NoelText Boxcis

NoelText Boxtrans


NoelText Boxopp dir

NoelText Boxopp dir

NoelText Boxcis


NoelText Boxtrans



13

The photochemical reaction proceeds by a conrotatory ring closure / opening mode and in

general a photostationary state is reached consisting of an equilibrium mixture of both the

hexatriene and cyclohexadiene (shown below).

Stereospecific thermal ring closure of triphenylhexatrienes.

HH

Ph

Ph

80 oC Ph

Phdis

HPh

H

Ph

Ph

Phdis

Ph Ph

Ph Ph

92 %

> 90 %

HPh

H

Ph Ph

dis> 90 %

110 oC 110 oC

Photochemical electrocyclic ring opening / closure of cyclohexdiene / hexatriene systems

HH

Me

Me

Me

Medis

h

Me

Me

Ph

Ph

hHH

Me

Me

Ph

Ph

Me

Me

Ph

Ph

hHMe

H

Me

Ph

Ph

NoelText Boxopp dir

NoelText Boxcis


NoelText Boxtrans

NoelText Boxopp dir

NoelText Boxtrans

NoelText Boxcis

NoelText Boxcon

NoelText Boxcon

NoelText Boxcis

NoelText Boxopp dir


NoelPencil



14

CYCLOADDITION REACTIONS

1. Reaction of two components to form a cyclic compound

2. Ring forming reactions

3. Pericyclic type both components are systems

4. Intramolecular and intermolecular versions

Classification

Based on the number of electrons involved in each component

The numbers are written within a square bracket e.g. [2 + 2], [2 + 4] etc

EXAMPLES OF CYCLOADDITION REACTIONS

+

O

O

H H

[2 + 2]

[4 + 2]

[4 + 4]

[4 + 6]

[14 + 2]

NC CN

NC CNNC CNCNCN

NoelCalloutin a triple bond the sigma bonds are formed by sp hybridised orbitals the remainig p orbitals are perpandicular to each other so at a time only one of the p orbitals can take part in the reaction so 2



15

Stereochemistry of cycloaddition reactions

Suprafacial and antarafacial approaches to a bond

suprafacial approach

syn addition

antarafacial approach

anti addition It is necessary to specify with respect to each component whether the approach is

suprafacial or antarafacial

The cycloaddition of ethylene to form cyclobutane is a [2s + 2s] process. The thermal

Diels-Alder reaction is a [4s + 2s] process

Frontier Orbital Method:

HOMO-LUMO interaction for a [2s+2s] cycloaddition.

LUMO

HOMO

both bonding

HOMO

LUMO

anti bonding

thermally forbidden

[2s + 2s]photochemically allowed

[2s + 2s]

[ethylene]*



16

HOMO-LUMO interaction for a [4s+2s] cycloaddition

[4s + 2s]thermally allowed

ethylene

butadiene

LUMO

HOMO

ethylene

butadiene

HOMO

LUMO

ethylene

[butadiene]*

LUMO

HOMO

antibonding

[4s + 2s]photochemically forbidden

Concerted [2+2] cycloaddition reactions of alkenes

*

1. Convenient way to form cyclobutanes

2. Reaction occurs from singlet excited -* state

3. Triplet sensitizer is required to form T1 state

4. Acyclic alkenes undergo competing cis-trans isomerization



17

5. Reaction is generally suprafacial-suprafacial additon and hence highly

stereospecific

Photochemical [2 + 2] Cycloadditions: The concerted photochemical [2 + 2] cycloaddition reaction is suprafacial on both of the systems. The dimerization of cis- and trans-2-butene have been reported to take place in a highly stereospecific manner. The structure of the four possible isomers are

given in Scheme below. The original 2-butene fragment in the product is shown by thick

lines. Only two isomers namely the cis-syn-cis (syn) and the cis-anti-cis (anti) isomer are

formed when pure cis 2-butene was photolysed in the liquid state. Similarly when pure

trans-2-butene was photolysed it gave only trans-anti-trans and cis-anti-cis isomers. The

fourth isomer, namely cis-anti-trans, was formed only when a mixture of cis- and trans-

2-butene was photolysed. This experiment clearly points to the fact that the reaction is

highly stereospecific and suprafacial in each of the reacting partners.

Photochemical cycloaddition reactions of cis- and trans-2-butene.

h+

anti / syn = 0.8

h +

direct

direct

+h

direct+ the above products

Chapman has reported an efficient photochemical cross addition of trans-stilbene with

tetramethylethylene with high quantum yield ( = 1.0) and high stereospecificity. The

inverse dependence of the rate of cycloaddition with temperature provided evidence for

an exciplex formation.



18

Photochemical cross addition of trans-stilbene and tetramethylethylene

Ph

Ph hvPh

+

Ph

[2+2] Photocycloadditions of cyclic alkenes

H

HH

h

sens = PhCOCH3

+

12 : 88

HH

H

HH

H

h+

hacetone

HH

H

Synthesis of cage structures by photochemical cycloaddition

HH

h

62 %cyclohexane

O

O

O

HH

hacetone

O

O

Obasketene

1. h2. H+

MeO OMe O

pentaprismane

Via exciplex, = 1.0



19

Diels-Alder Reaction:

Thermal cycloaddition between a cisoid conjugated diene and a dienophile, usually a

olefin or an acetylene

Six membered ring is formed

It is a concerted [4s + 2s ] addition

R2

R1

+CHR3CHR4

***

*

Diels-Alder Diene

s-cisoid s-transoid

transoid cisoidconjugated transoid dienes

>> > >

Order of reactivity of cyclic conjugated dienes



20

Dienophiles:

CN

CN

CN CNNC CNNC

NC CN

COCH3O

O

O

COOCH3 COOCH3

COOCH3

NN

N-Ph

O

O

O

O

The cis rule :

R

R

R

R

COOEt

COOEt

COOEt

COOEt

COOEt

COOEt

R

R

H

H

COOEt

COOEt

R

H

H

R

OO OR

R

H

H

O

O

O

H

H

OO OR

H

H

R

O

O

O

H

H

R = Me, Ph

R = Me, Ph



21

COOH

COOH

HOOC

COOH

COOHCOOH

COOH

COOH

Me

Me

Me

Me

Me H

HMe

HCOOHCOOH

H

Me H

HMe

COOHHCOOH

H

Alders endo rule (secondary orbital interactions):

rt+

HH

Ort

+

O

HH

O

OO

O

O

O OO

HOMO

LUMO



22

Regioselectivity in Diels-Alder reaction:

R

+R'

RR'

R

R'+

"ortho" "meta"

+R' R'

R'+

R R R

"meta" "para"

Diels-Alder reactions are highly ortho/para selective.

The regioselectivity in Diels-Alder reactions is exemplified below

R

+

X

RX

R

X

R X ortho metaMe COOMe 89 : 11OAc COOMe 100 : 0OMe COOMe 100 : 0OMe CN 100 : 0OMe CHO 100 : 0

R+

X R

X

R X+

R X para : metaMe COOMe 80 : 20Me CHO 100 : 0OMe COMe 100 : 0OMe CHO 100 : 0

ELECTROCYCLIC REACTIONSWoodward Hoffmann rules for electrocyclic reactions

CYCLOADDITION REACTIONS

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