Insights into the mechanism, selectivity, and substituent effects in the Diels-Alder reaction of azatrienes with electron-rich dienophiles: An MEDT study.

Autor: Rafik A; Laboratory of Spectroscopy, Molecular Modeling, Materials, Nanomaterials, Water and Environment, LS3MN2E/CERNE2D, Faculty of Sciences, Mohammed V University in Rabat, Morocco; Departamento de Ciencias Integradas, Centro de Estudios Avanzados en Física, Matemática y Computación, Unidad Asociada GIFMAN, CSIC-UHU, Universidad de Huelva, Huelva, 21071, Spain., Jaddi A; Laboratory of Spectroscopy, Molecular Modeling, Materials, Nanomaterials, Water and Environment, LS3MN2E/CERNE2D, Faculty of Sciences, Mohammed V University in Rabat, Morocco., Salah M; Molecular Modelling and Spectroscopy Research Team, Faculty of Science, Chouaïb Doukkali University, P.O. Box 20, 24000, El Jadida, Morocco., Komiha N; Laboratory of Spectroscopy, Molecular Modeling, Materials, Nanomaterials, Water and Environment, LS3MN2E/CERNE2D, Faculty of Sciences, Mohammed V University in Rabat, Morocco., Carvajal M; Departamento de Ciencias Integradas, Centro de Estudios Avanzados en Física, Matemática y Computación, Unidad Asociada GIFMAN, CSIC-UHU, Universidad de Huelva, Huelva, 21071, Spain., Marakchi K; Laboratory of Spectroscopy, Molecular Modeling, Materials, Nanomaterials, Water and Environment, LS3MN2E/CERNE2D, Faculty of Sciences, Mohammed V University in Rabat, Morocco. Electronic address: k.marakchi@um5r.ac.ma.
Jazyk: angličtina
Zdroj: Journal of molecular graphics & modelling [J Mol Graph Model] 2024 Nov; Vol. 132, pp. 108819. Date of Electronic Publication: 2024 Jul 18.
DOI: 10.1016/j.jmgm.2024.108819
Abstrakt: The reactivity and mechanistic intricacies of azatrienes in Diels-Alder reactions have been relatively unexplored despite their intriguing potential applications. In this study, we employ Molecular Electron Density Theory to theoretically investigate the hetero-Diels-Alder reaction involving azatrienes with ethyl vinyl ether and allenyl methyl ether. Analysis of Conceptual Density Functional Theory, energetic profiles, and the topological characteristics is conducted to elucidate the reactions. The revealed mechanism manifests as a polar one-step two-stages process under kinetic control. We establish a clear relationship of between the periselectivity, regioselectivity, and stereoselectivity on one hand and the characteristics of the reactions mechanism on the other hand. The influence of weak interactions on reaction activation barriers and bonding evolution are discussed in detail. We demonstrate that substituents enhancing the reverse electron density flux facilitate the feasibility of the reactions. The results lay ground for a meticulous control of the reaction of azatriene in similar synthetic scenarios.
Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Khadija Marakchi reports financial support was provided by European Union. Miguel Carvajal reports financial support was provided by European Union. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
(Copyright © 2024 Elsevier Inc. All rights reserved.)
Databáze: MEDLINE
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