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Molecules 2018, 23(8), 1913; https://doi.org/10.3390/molecules23081913

A Molecular Electron Density Theory Study of the Competitiveness of Polar Diels–Alder and Polar Alder-ene Reactions

1
Department of Organic Chemistry, University of Valencia, Moliner 50, 46100 Valencia, Spain
2
Facultad de Ciencias Exactas, Departamento de Ciencias Químicas, Universidad Andres Bello, Av. República 498, Santiago 8370146, Chile
*
Author to whom correspondence should be addressed.
Received: 16 July 2018 / Revised: 27 July 2018 / Accepted: 28 July 2018 / Published: 31 July 2018
(This article belongs to the Special Issue Theoretical Investigations of Reaction Mechanisms)
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Abstract

The competitiveness of the BF3 Lewis acid (LA) catalyzed polar Diels–Alder (P-DA) and polar Alder-ene (P-AE) reactions of 2-methyl-1,3-butadiene, a diene possessing an allylic hydrogen, with formaldehyde has been studied within the Molecular Electron Density Theory (MEDT) at the MPWB1K/6-311G(d,p) computational level. Coordination of BF3 LA to the oxygen of formaldehyde drastically accelerates both reactions given the high electrophilic character of the BF3:formaldehyde complex. As a consequence, these reactions present a very low activation enthalpy—less than 2.2 kcal·mol−1—thus becoming competitive. In dioxane, the P-AE reaction is slightly favored because of the larger polar character of the corresponding transition state structure (TS). In addition, the Prins reaction between hexahydrophenanthrene and the BF3:formaldehyde complex has also been studied as a computational model of an experimental P-AE reaction. For this LA-catalyzed reaction, the P-DA reaction presents very high activation energy because of the aromatic character of the dienic framework. The present MEDT study allows establishing the similarity of the TSs associated with the formation of the C–C single bond in both reactions, as well as the competitiveness between P-AE and P-DA reactions when the diene substrate possesses at least one allylic hydrogen, thus making it necessary to be considered by experimentalists in highly polar processes. In this work, the term “pseudocyclic selectivity” is suggested to connote the selective formation of structural isomers through stereoisomeric pseudocyclic TSs. View Full-Text
Keywords: Molecular Electron Density Theory; Diels-Alder reactions; Alder-ene reactions; competitive reactions; polar reactions; Prins reaction; pseudocyclic selectivity Molecular Electron Density Theory; Diels-Alder reactions; Alder-ene reactions; competitive reactions; polar reactions; Prins reaction; pseudocyclic selectivity
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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. (CC BY 4.0).

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Domingo, L.R.; Ríos-Gutiérrez, M.; Pérez, P. A Molecular Electron Density Theory Study of the Competitiveness of Polar Diels–Alder and Polar Alder-ene Reactions. Molecules 2018, 23, 1913.

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