Version 1
: Received: 17 September 2024 / Approved: 17 September 2024 / Online: 17 September 2024 (16:49:30 CEST)
How to cite:
Bouhaoui, A.; Moumad, A.; Domingo, L. R.; Bouissane, L. A MEDT Study of the Reaction Mechanism and Selectivity of the Hetero Diels-Alder Reaction between 3-Methylene-2,4-chromandione and Methyl Vinyl Ether. Preprints2024, 2024091343. https://doi.org/10.20944/preprints202409.1343.v1
Bouhaoui, A.; Moumad, A.; Domingo, L. R.; Bouissane, L. A MEDT Study of the Reaction Mechanism and Selectivity of the Hetero Diels-Alder Reaction between 3-Methylene-2,4-chromandione and Methyl Vinyl Ether. Preprints 2024, 2024091343. https://doi.org/10.20944/preprints202409.1343.v1
Bouhaoui, A.; Moumad, A.; Domingo, L. R.; Bouissane, L. A MEDT Study of the Reaction Mechanism and Selectivity of the Hetero Diels-Alder Reaction between 3-Methylene-2,4-chromandione and Methyl Vinyl Ether. Preprints2024, 2024091343. https://doi.org/10.20944/preprints202409.1343.v1
APA Style
Bouhaoui, A., Moumad, A., Domingo, L. R., & Bouissane, L. (2024). A MEDT Study of the Reaction Mechanism and Selectivity of the Hetero Diels-Alder Reaction between 3-Methylene-2,4-chromandione and Methyl Vinyl Ether. Preprints. https://doi.org/10.20944/preprints202409.1343.v1
Chicago/Turabian Style
Bouhaoui, A., Luis Ramon Domingo and Latifa Bouissane. 2024 "A MEDT Study of the Reaction Mechanism and Selectivity of the Hetero Diels-Alder Reaction between 3-Methylene-2,4-chromandione and Methyl Vinyl Ether" Preprints. https://doi.org/10.20944/preprints202409.1343.v1
Abstract
The hetero Diels-Alder (HDA) reaction between the ambident heterodiene 3-methylene-2,4-chromandione (MCDO) and the non-symmetric methyl vinyl ether (MVE) is investigated within the Molecular Electron Density Theory (MEDT) at the B3LYP/6-311G(d,p) computational level. The aim of this study is to gain insight into the molecular mechanism and to elucidate the factors that control the selectivity found experimentally. DFT-based reactivity indices reveal that MCDO exhibits strong electrophilic character, while MVE displays a strong nucleophilic character. Meanwhile, Parr function explains the ortho regioselectivity of this HDA reaction. The highly polar nature of this HDA reaction, supported by the high global electron density transfer (GEDT) taking place at the transition state structures (TSs), accounts for the very low activation energy associated with the most favorable TS-4on. The ambident nature of MCDO allows the formation of two constitutional isomeric cycloadduct. In the case of MVE, the pseudocyclic selectivity is attained by a thermodynamic control. This polar HDA reaction displays an endo stereoselectivity and a complete ortho regioselectivity. A comparative Relative Interacting Atomic Energy (RIAE) analysis of the two diastereomeric TS-4on and TS-6on indicates a highly likeness between them, which explains the low pseudocyclic selectivity under kinetic control.
Keywords
Molecular Electron Density Theory; Hetero Diels-Alder; ambident heterodiene; 3-methylene-2,4-chromandione; methyl vinyl ether; pseudocyclic selectivity; Relative Interacting Atomic Energy
Subject
Chemistry and Materials Science, Organic Chemistry
Copyright:
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
