Unveiling the lewis acid catalyzed diels-alder reactions through the molecular electron density theory
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Archivos
Fecha
2020-06
Profesor/a Guía
Facultad/escuela
Idioma
en_US
Título de la revista
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Título del volumen
Editor
MDPI AG
Nombre de Curso
Licencia CC
ATRIBUCIÓN 4.0 INTERNACIONAL
Licencia CC
https://www.mdpi.com/1420-3049/25/11/2535
Resumen
The effects of metal-based Lewis acid (LA) catalysts on the reaction rate and regioselectivity in polar Diels-Alder (P-DA) reactions has been analyzed within the molecular electron density theory (MEDT). A clear linear correlation between the reduction of the activation energies and the increase of the polar character of the reactions measured by analysis of the global electron density transfer at the corresponding transition state structures (TS) is found, a behavior easily predictable by analysis of the electrophilicity ω and nucleophilicity N indices of the reagents. The presence of a strong electron-releasing group in the diene changes the mechanism of these P-DA reactions from a two-stage one-step to a two-step one via formation of a zwitterionic intermediate. However, this change in the reaction mechanism does not have any chemical relevance. This MEDT study makes it possible to establish that the more favorable nucleophilic/electrophilic interactions taking place at the TSs of LA catalyzed P-DA reactions are responsible for the high acceleration and complete regioselectivity experimentally observed.
Notas
Indexación: Scopus.
Palabras clave
Catalysis, Diels-Alder, Lewis acid, Molecular electron density theory, Relation mechanism
Citación
Molecules Volume 25, Issue 11June 2020 Article number 2535
DOI
10.3390/molecules25112535