A molecular electron density theory study of the competitiveness of polar diels–alder and polar alder-ene reactions

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dc.contributor.authorDomingo, L.R.
dc.contributor.authorRíos-Gutiérrez, M.
dc.contributor.authorPérez, P.
dc.date.accessioned2019-11-29T17:47:46Z
dc.date.available2019-11-29T17:47:46Z
dc.date.issued2018
dc.descriptionIndexación: Scopus.es
dc.descriptionFunding: Ministry of Economy and Competitiveness (MINECO) of the Spanish Government, project CTQ2016-78669-P (AEI/FEDER, UE) and Fondecyt (Chile) grant 1180348.
dc.descriptionAcknowledgments: This research was supported by the Ministry of Economy and Competitiveness (MINECO) of the Spanish Government, project CTQ2016-78669-P (AEI/FEDER, UE) and Fondecyt (Chile) grant 1180348. L.R.D. thanks Fondecyt for continuous support through Cooperación Internacional. M.R.-G. also thanks MINECO for a post-doctoral contract cofinanced by the European Social Fund (BES-2014-068258).
dc.description.abstractThe 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. © 2018 by the authors.es
dc.description.urihttps://www.mdpi.com/1420-3049/23/8/1913
dc.identifier.citationMolecules, 23(8), art. no. 1913.es
dc.identifier.issn1420-3049
dc.identifier.otherDOI: 10.3390/molecules23081913
dc.identifier.urihttp://repositorio.unab.cl/xmlui/handle/ria/10925
dc.language.isoenes
dc.publisherMDPI AGes
dc.subjectDiels-Alder reactionses
dc.subjectAlder-ene reactionses
dc.subjectCompetitive reactionses
dc.subjectMolecular Electron Density Theoryes
dc.subjectPolar reactionses
dc.subjectPrins reactiones
dc.subjectPseudocyclic selectivityes
dc.titleA molecular electron density theory study of the competitiveness of polar diels–alder and polar alder-ene reactionses
dc.typeArtículoes
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