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Keywords = ambident heterodiene

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15 pages, 2781 KiB  
Article
An MEDT Study of the Reaction Mechanism and Selectivity of the Hetero-Diels–Alder Reaction Between 3-Methylene-2,4-Chromandione and Methyl Vinyl Ether
by Abderrazzak Bouhaoui, Aziz Moumad, Luis R. Domingo and Latifa Bouissane
Molecules 2024, 29(21), 5109; https://doi.org/10.3390/molecules29215109 - 29 Oct 2024
Cited by 1 | Viewed by 1110
Abstract
The hetero-Diels–Alder (HDA) reaction between the ambident heterodiene 3-methylene-2,4-chromandione (MCDO) and non-symmetric methyl vinyl ether (MVE) is investigated using 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 its molecular mechanism [...] Read more.
The hetero-Diels–Alder (HDA) reaction between the ambident heterodiene 3-methylene-2,4-chromandione (MCDO) and non-symmetric methyl vinyl ether (MVE) is investigated using 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 its molecular mechanism and to elucidate the factors that control the selectivity found experimentally. DFT-based reactivity indices reveal that MCDO exhibits strong electrophilic characteristics, while MVE displays a strong nucleophilic character. Meanwhile, the 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 for the formation of two constitutional isomeric cycloadducts. In the case of MVE, pseudocyclic selectivity is attained using 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 structures TS-4on and TS-6on indicates a high degree of likeness, which explains the low pseudocyclic selectivity under kinetic control. Full article
(This article belongs to the Special Issue Feature Papers in Computational and Theoretical Chemistry)
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