期刊
MOLECULES
卷 23, 期 8, 页码 -出版社
MDPI
DOI: 10.3390/molecules23081913
关键词
Molecular Electron Density Theory; Diels-Alder reactions; Alder-ene reactions; competitive reactions; polar reactions; Prins reaction; pseudocyclic selectivity
资金
- Ministry of Economy and Competitiveness (MINECO) of the Spanish Government [CTQ2016-78669-P]
- Fondecyt (Chile) [1180348]
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.
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