Lewis Acid-Catalyzed Carbonyl-Ene Reaction: Interplay between Aromaticity, Synchronicity, and Pauli Repulsion

The physical factors governing the catalysis in Lewis acid-promoted carbonyl-ene reactions have been explored in detail quantum chemically. It is found that the binding of a Lewis acid to the carbonyl group directly involved in the transformation greatly accelerates the reaction by decreasing the corresponding activation barrier up to 25 kcal/mol. The Lewis acid makes the process much more asynchronous and the corresponding transition state less in-plane aromatic. The remarkable acceleration induced by the catalyst is ascribed, by means of the activation strain model and the energy decomposition analysis methods, mainly to a significant reduction of the Pauli repulsion between the key occupied π-molecular orbitals of the reactants and not to the widely accepted stabilization of the LUMO of the enophile.

Bibliographic Details

Main Authors:	Rodríguez, Humberto A., Cruz, Daniel A., Padrón, Juan I., Fernández, Israel
Other Authors:	Ministerio de Ciencia e Innovación (España)
Format:	artículo biblioteca
Language:	English
Published:	ACS Publications 2023-07-24
Subjects:	Addition reactions, carbonyls, chemical reactions, Lewis acids, transfer reactions,
Online Access:	http://hdl.handle.net/10261/334735
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