Electrocyclic Reactions

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
Organic reactions: Broad Classification
Organic reactions
Polar reactions Radical reactions Pericyclic reactions

 Reaction of Nucleophile  Reaction of Radical  Electrons in the reactant(s)
and electrophile are reorganized in a cyclic
manner
Pericyclic reaction: Classification
 Electrocyclic reactions
• Rearrangement of π-electrons in an open conjugated thermal
D
system to cyclic product
• One new σ-bond is formed in the expense of a π-bond
• Ring-closure/ring-opening (retro-electrocyclic reaction)
 Cycloaddition reactions
• Addition of two π-system to form cyclic product
thermal
• Two new σ-bonds are formed at the expense of two π-
bonds
• Backward reaction is referred as retro-cycloaddition or
cycloreversion
 Sigmatropic rearrangements
• Movement of σ-bond from one position to another thermal
D
with accompanying rearrangement of π-bonds
• Concerted unimolecular isomerization
• No change in the number of σ & π-bonds
Pericyclic reactions
Electrocyclic reactions
Cycloadditions
Sigmatropic rearrangement
 Reactions of Conjugated polyenes

 Takes place under thermal and photochemical conditions.
 Controlled by orbital symmetry; Stereospecific.
 generally Unaffected by solvents & other additives
 Concerted – Cyclic transition state
 The breaking and making of bonds (σ & π) occur
simultaneously in a cyclic transition state
Electrocyclic reactions
Ring opening or closing
 or h
Exothermic by 11 kcal/mol
Rules for Pericyclic Reactions
Woodward-Hoffmann rules:
“Symmetries of the reactant MOs are the same as those
of the product” – Conservation of Orbital Symmetry
Lobes of the reactant MOs must possess the correct sign

for the bonding to occur in the TS leading to product R. B. Woodward R. Hoffmann
Symmetries of Reactants & Products match → Correlate (Symmetry Allowed)

Symmetries of R & P do not match → Don’t correlate (Symmetry Forbidden)
Kenichi Fukui
Fukui’s FMO Theory:
“We only have to look at the FMOs; i.e., HOMO and LUMO”
Electrocyclic Reaction
• Rearrangement of π-electrons in an open conjugated system to cyclic
product
• One new σ-bond is formed at the expense of a π-bond
• Cyclic transition state involves either 4n or 4n+2 electrons
• Ring-closure/ring-opening (retro-electrocyclic reaction)
(6π system)
(4π system)
• Stereochemistry of an electrocyclic reaction is determined by the symmetry of
the polyene HOMO
Thermal electrocyclic ring closure
p2
Bonding interaction is maximum on conrotation
Lobes of the reactant MOs must possess the correct sign for the bonding to occur in the TS
leading to product
Photochemical ring closure
p3
Disrotation gives maximum bonding overlap

Modes of ring opening or closing
E,E
 h
Con Dis
Trans Cis
What happens if we change the geometry of the alkene. Ie. E,Z ?
Electrocyclic ring-opening: Cyclobutene system
Due to steric reason!

This is an example of a thermally (conrotation) forbidden (hence the stability);
Disrotatory ring opening (photochemically allowed)
What is the most suitable condition to convert Dewar benzene to benzene?
Thermal or photochemical
Electrocyclic ring-opening: Cyclobutene system
Δ (175oC) hν
Δ (175oC) hν
Stereoselective thermal isomerization
?
Conrotatory ring closure
occurs in this case as it
relieves the strain due to
trans olefin in the frame-work
Ring opening (thermal) in conrotatory mode gives cis-trans cycloheptadiene

which suffer from significant strain, hence the stability
Cis-trans
bicycloheptene (proceeds via diradicals)
(strain)
4 3
If electrocyclic ring opening of 2 and 3 is considered, which one will undergo

faster ring opening? Why?
E,Z,E
 h
Dis Con
Trans
Cis
Trienes MO Picture
Cis
Trans
Construction of Molecular Orbitals (thermal condition)
Ѱ6
Ѱ4
Ѱ2 Ѱ5
LUMO
Ѱ3 LUMO
Ѱ4
HOMO
Ѱ3
HOMO
Ѱ2
Ѱ1 Ѱ2
Ѱ1
Ѱ1
2π 4π 6π
Molecular Orbitals (photochemical condition)
Ѱ6
Ѱ4 LUMO
Ѱ5 LUMO
Ѱ3 HOMO
Ѱ4 HOMO
Ѱ3
Ѱ2
Ѱ2
Ѱ1
Ѱ1
4π
6π
Rules for electrocyclic reactions
Woodward-Hofmann
n = 1, 2, 3  h
4n CON DIS
4n+2 DIS CON

Electrocyclic Reaction (ring closing)
Smooth reaction
disrotatory
no reaction
conrotator
y
Small ring with trans-ring fusion
Large strain, not formed
Identify X in the following
Suggest mechanism for the following with particular relevance to the

stereochemical outcome
Electrocyclic Reaction: Examples
Electrocyclic Reaction: Examples
 H
Why the same product is
formed under both
thermal and photo-
h chemical conditions?
H rationalize.
Example of valance tautomerism

(only involve reorganization of bonding e’s)
Ea = 7 kcal/mol for R = -COOCH3
write the ring closure

* Sequences that lead to
the final product
under thermal
Conditions.
What is the orientation
of bridgehead hydrogens *
R H
H R

H
H R
R h
H H
R R
Question
Draw the molecular orbitals of this tetraene and rationalize the observation
using the orbital symmetries of frontier orbitals under thermal and
photochemical conditions; (note yn will have n-1 nodes)
Question
100 °C hv 25 °C
? ? ?
H
1,3,5-cyclononatriene
H
There is an electrocyclic reaction
happening right on our skin (epidermis)!
Vitamin D deficiency can cause Rickets, Osteomalacia

Osteoporosis etc.
Question
Show all intermediate steps with correct stereochemistry in the following transformations
photochemical
thermal
Electrocyclic Reaction: Triene system
Predict the products with correct stereochemistry

Electrocyclic Reactions

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CY 1001

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

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

Polar reactions Radical reactions Pericyclic reactions

 Reactions of Conjugated polyenes

Lobes of the reactant MOs must possess the correct sign

Symmetries of Reactants & Products match → Correlate (Symmetry Allowed)

Bonding interaction is maximum on conrotation

Disrotation gives maximum bonding overlap

Due to steric reason!

Stereoselective thermal isomerization

Ring opening (thermal) in conrotatory mode gives cis-trans cycloheptadiene

If electrocyclic ring opening of 2 and 3 is considered, which one will undergo

4n+2 DIS CON

Suggest mechanism for the following with particular relevance to the

Example of valance tautomerism

Ea = 7 kcal/mol for R = -COOCH3

write the ring closure

Vitamin D deficiency can cause Rickets, Osteomalacia

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