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FMO and PMO Approaches in Pericyclic Reactions

The document discusses pericyclic reactions, which are concerted reactions characterized by a cyclic transition state and include four major types: electrocyclic, cycloaddition, sigmatropic, and group transfer reactions. It introduces two approaches for predicting stereochemistry based on molecular orbital symmetry: the Frontier Molecular Orbital (FMO) approach and the Perturbed Molecular Orbital (PMO) approach, detailing their applications in various reactions. Additionally, it explains the role of molecular orbitals in conjugated systems and the significance of aromaticity in determining reaction pathways under thermal and photochemical conditions.

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94 views10 pages

FMO and PMO Approaches in Pericyclic Reactions

The document discusses pericyclic reactions, which are concerted reactions characterized by a cyclic transition state and include four major types: electrocyclic, cycloaddition, sigmatropic, and group transfer reactions. It introduces two approaches for predicting stereochemistry based on molecular orbital symmetry: the Frontier Molecular Orbital (FMO) approach and the Perturbed Molecular Orbital (PMO) approach, detailing their applications in various reactions. Additionally, it explains the role of molecular orbitals in conjugated systems and the significance of aromaticity in determining reaction pathways under thermal and photochemical conditions.

Uploaded by

jassawarrior696
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We take content rights seriously. If you suspect this is your content, claim it here.
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FMO and PMO approach

NAME – JAGJEET SINGH


CLASS – [Link]. CHEMISTRY 2ND SEMESTER
COLLEGE- Dr B. R. AMBEDKAR GOVT PG
COLLEGE, SGNR
SUBMITTED TO -
Introduction to Pericyclic
Reactions
• Pericyclic reactions are concerted reactions involving a
reorganization of electrons through a cyclic transition state,
without the formation of intermediates.
• These reactions are activated by either thermally (heat) or
photochemically (light).
• There are 4 major types of pericyclic reaction :-
 Electrocyclic Reactions
 Cycloaddition Reactions
 Sigmatropic Reactions
 Group Transfer Reactions
Features of Pericyclic Reaction

• Concerted mechanism, which means bond breaks and forms


simultaneously.
• Electron moves in a closed loop, results in cyclic transition state.
• These reactions are stereospecific in nature.
• Orbital symmetry is the key factor determining product’s stereochemistry.
• There are two appraoches which predict the stereochemistry of product
and are based on molecular orbital symmetry:-

 Frontier molecular orbital (FMO) approach


 Perturbed molecular orbital ( PMO ) appraoch
Molecular Orbitals in Conjugated Systems
In conjugated systems, the p-orbitals overlap to form molecular orbitals (MOs) with different
energies. These MOs are arranged in order of increasing nodes, with the lowest energy orbital
having no nodes and the highest having the most
The number of nodes increases with energy; if the number of nodes is even, terminal orbitals are in
the same phase, and if odd, they are in opposite phases.
The highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital
(LUMO) play a key role in determining chemical reactivity.
FMO Approach
• In this approach, the terminal orbitals act as the HOMO and LUMO, and
their interaction drives the reaction.
• This appraoch can be applied to electrocyclic, cycloaddition ad sigmatropic
reactions.
This example is Diels- alder reaction, which is a famous cycloaddition reaction.

This reaction is allowed in thermal condition.

In the thermal pathway, the HOMO of the diene overlaps with the LUMO of the
dienophile in-phase at both bonding sites.

The reaction follows a π₄ˢ + π₂ˢ pathway, involving suprafacial overlap of both the
diene and dienophile π-systems.
PMO Approach
• Analyzes pericyclic reactions using aromaticity rules of the
transition state
• According to Hückel’s rule, a planar conjugated system with (4n+2) π-
electrons is aromatic and stable, while one with 4n π-electrons is
antiaromatic and unstable in the ground state.
• When a cyclic system has a node or an odd number of nodes in its orbital
arrangement, the aromaticity rules reverse: a (4n+2) π-electron system
with one node becomes antiaromatic in the ground state, while a 4nπ-
electron system with one node becomes aromatic.
• Under thermal conditions, aromatic transition states are allowed while
antiaromatic ones are forbidden; in photochemical conditions, this
relationship is reversed.
Electrocyclization (Cyclobutene ⇌ 1,3-Butadiene)

In 4 π-electron systems, one node → aromatic (thermally allowed,


conrotatory).

Zero nodes → antiaromatic (photochemically allowed, disrotatory).


Combines diene (4 π) and alkene (2 π) orbitals into a single cyclic
array.
Thermal: no node, 6 π-electrons → aromatic transition state,
symmetry-allowed.

Photochemical: one node → antiaromatic, reaction only allowed


under light.

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