CY 1001

Aromaticity: Electron delocalization, resonance and aromaticity; Story of cyclic

molecular oribital description of aromaticity and anti-aromaticity, polyenes

annulenes; ring current, NMR as a tool, diamagnetic anisotropy

Aromatic electrophilic and nucleophilic substitutions, benzyne;
reaction mechanisms, reactivity and orientation.

Special reactivities
Pericyclic reactions: Definition, classification, electrocyclic, of conjugated
systems
cycloaddition, sigmatropic reactions, electrocyclic reactions,
examples of ring closing and ring opening reactions of butadiene
and hexatriene only; cycloaddition reactions: Diels Alder reaction;
Woodward Hoffmann rules, FMO approach stereochemical aspects
and synthetic utility of the above reactions, sigmatropic rearrangement
limited to Cope and Claisen rearrangements.

Quiz – 50 marks
Stability of cyclobutadiene

1.567Ao

1.346 Ao
Cycloadditions

Diels-Alder Reaction
• Otto Diels, Kurt Alder; Nobel prize, 1950
• Leads to cyclohexene ring
• Diene (enophile) + alkene (or alkyne) with electron-
withdrawing group (dienophile)

Arrows are given for representation only; Bond migration do not happen like that
Stereo-chemical Requirements

Diene must be in cis conformation.

It’s C1 and C4 p orbitals must overlap with the p orbitals of dienophile.

Both sigma bonds are on same face of the diene: syn stereochemistry.

stereochemistry (configuration) in reacting partners get directly

transferred to products
 Naming
[2π + 2π]
+

[4π + 2π]

[4π + 4π]
suprafacial antarafacial
approach approach

syn addition anti addition

[4π + 6π]
O

O
[2πs + 2πs]
[14π + 2π]
[4πs + 2πs]
NC CN H H
NC CN
CN CN
NC CN
 Conformations of the Diene
1 1

4
4
s-cis conformation s-trans conformation
Trans stable by 12 kJ/mol (2.8 kcal/mol).
Examples
 H COOEt
H
COOEt

Stereochemistry +

COOEt COOEt
H
H

H COOEt
H
COOEt

H H
EtOOC
stereochemistry (configuration) EtOOC
CH 3
in reacting partners get directly CH 3 H

transferred to products
H
+
H
H

CH 3 CH 3

CH 3 CH 3
H

H
+
CH3
CH3

H H
CH 3 H 3C H

H H CN CN

+ H

H H CH 3

CH3 H CN CN

+ H

H
H
H
H3 C
H 3C NC
H
CN

CH 3
CH3
H
H H
NC
H
CN
HOMO 4πa
4πs

LUMO 2πs 2πa

thermal

4πs 4πa

2πa photochemical 2πs

What happens if you take LUMO of enophile and HOMO of ene?

Generally, the electron rich species reacts via its HOMO

and the electron poor species via its LUMO.
 Photochemical 4+2 (rare)
H
R
R R
hν
H H
H
R H
H
2πs 2πa

2πs 2πa
photochemical

2πa 2πs

2πs
thermal 2πa
Thermal 2+2
O
O
∆
C +

CH 2
Thermal 2+2

stereochemistry
[2 + 2] Cycloaddition

UV light, –65°C, 44 hours, 77% yield.

Photochemically allowed, but thermally forbidden

Stereochemistry—Alder/Stein Rules (1937)
The “cis-principle” – The relative stereochemistry of each of the components is
retained in the product. Ie, a dienophile with a ‘cis’ arrangement of substituents will
lead to a product with ‘cis’ arrangement of substituents in the adduct (similarly trans)

The Diels-Alder reaction is suprafacial in each reacting component

it is a stereospecifific reaction

The “endo rule” applies. The secondary bonding interaction between pi system
of the diene can overlap with the pi system of the substituent in the dienophile to
give preference for an endo product (under kinetic conditions)
 Endo Rule
The p orbitals of the electron-withdrawing groups on the dienophile have
a secondary overlap with the p orbitals of C2 and C3 in the diene.
Secondary orbital overlap favors the endo- product
The endo-rule applies only to kinetic conditions

Under reversible thermodynamic conditions, the more stable product is favored

(often exo)
 Stereo-selectivity

Regio-selectivity
Regio--selectivity of Diels
Regio Diels--Alder Reaction

‘Ortho’- or ‘Para’- Selectivity (1,2- or 1,4- but not 1,3-)

D W
Not

1,3-product
Reason for regioselectivity..

In addition to orbital symmetry (phases), orbitals tend to interact with orbitals

with similar coefficient
Ref. NPTEL Notes, SSR
Method to prepare 1,3 product

O2N NO2 REDUCTION

+
CO2Me RO CO2Me R3SnH RO CO2Me
RO

In β-nitro-α-unsaturated ketones and esters, the nitro group controls the orientation of
addition.
 hν
+
direct
anti / syn = 0.8

hν
+
direct

hν
+ + the above products
direct

Ph Ph
Ph hv, benzene Ph Ph
+
27 % conversion Ph
Ph Ph
Ph Ph
4:1

Rationalize the above observations

 Give reason for the differences in the yields

How many, and what are the steps involved

in the following transformation

∆
 ?

Predict whether it is
Thermal or photochemical?

O
O O

Example for an application

Diels Alder reaction application
Cycloaddition in synthesis examples

H
H hν
cyclohexane
62 %

O O O
H H
H O

∆
O
H
O
[2π + 2π] hν

Pb(OAc)4 H
H O

basketene O

O
thermal
Thermal isomerization of benzocyclobutene to ortho quinodimethane
 O O

R +
R
H

O O
R
+

R
Nicolaou, K. C. J. Am. Chem. Soc. 1982, 104, 5555; J. Am. Chem. Soc. 1982, 104, 5557;
J. Am. Chem. Soc. 1982, 104, 5558; J. Am. Chem. Soc. 1982, 104, 5560.
“Symmetry forbidden” Cycloaddition

[2 + 2] cycloaddition of two ethylenes to form cyclobutane

has anti-bonding overlap of HOMO and LUMO.
Photochemical activation

Absorption of correct energy photon will promote an electron to an energy

level that was previously unoccupied (LUMO), which would become the
new HOMO.
H3CO H3CO
CH2
+
HC H
C CHO
O para
The relative amounts of the regioisomeric products formed in the Diels–Alder
reaction are strongly influenced by Lewis acid catalysts

With 2,3-disubstituted butadienes, the structure of the adducts obtained will depend on
the nature of the two substituents

Here, the phenylthio substituent has a stronger directing effect than the methoxy group