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.
| Main Authors: | , , , |
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| Other Authors: | |
| Format: | artículo biblioteca |
| Language: | English |
| Published: |
ACS Publications
2023-07-24
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| Subjects: | Addition reactions, carbonyls, chemical reactions, Lewis acids, transfer reactions, |
| Online Access: | http://hdl.handle.net/10261/334735 |
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