RT Journal Article
T1 Insights into the mechanism, selectivity, and substituent effects in the Diels-Alder reaction of azatrienes with electron-rich dienophiles: An MEDT study
A1 Rafik, Amine
A1 Jaddi, Abdeljabbar
A1 Salah, Mohammed
A1 Komiha, Najia
A1 Carvajal Zaera, Miguel
A1 Marakchi, Khadija
AB 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.
PB Elsevier
SN 1093-3263
YR 2024
FD 2024
LK https://hdl.handle.net/10272/24071
UL https://hdl.handle.net/10272/24071
LA eng
NO Rafik, A., Jaddi, A., Salah, M., Komiha, N., Carvajal, M., & Marakchi, K. (2024). Insights into the mechanism, selectivity, and substituent effects in the Diels-Alder reaction of azatrienes with electron-rich dienophiles: An MEDT study. In Journal of Molecular Graphics and Modelling (Vol. 132, p. 108819). Elsevier BV. https://doi.org/10.1016/j.jmgm.2024.108819
NO This work has received funding from the European Union's Horizon 2020 research and innovation program under Marie Sklodowska-Curie grant agreement No. 872081, and grant PID2022-136228NB-C21 funded by MICIU/AEI/10.13039/501100011033 and, as appropriate, by ERDF A way of making Europe, by ERDF/EU, by the European Union or by the European Union NextGenerationEU/PRTR. The authors acknowledge the Moroccan Association of Theoretical Chemists for providing the computational programs.
DS Repositorio Institucional de la Universidad de Huelva
RD 1 jun 2026