On the catalytic effect of water in the intramolecular diels-alder reaction of quinone systems: A theoretical study

Soto Delgado Jorge, Arie Aizman, Renato Contreras, Luis R. Domingo

Producción científica: Contribución a una revistaArtículorevisión exhaustiva

15 Citas (Scopus)

Resumen

The mechanism of the intramolecular Diels-Alder (IMDA) reaction of benzoquinone 1, in the absence and in the presence of three water molecules, 1w, has been studied by means of density functional theory (DFT) methods, using the M05-2X and B3LYP functionals for exploration of the potential energy surface (PES). The energy and geometrical results obtained are complemented with a population analysis using the NBO method, and an analysis based on the global, local and group electrophilicity and nucleophilicity indices. Both implicit and explicit solvation emphasize the increase of the polarity of the reaction and the reduction of activation free energies associated with the transition states (TSs) of this IMDA process. These results are reinforced by the analysis of the reactivity indices derived from the conceptual DFT, which show that the increase of the electrophilicity of the quinone framework by the hydrogen-bond formation correctly explains the high polar character of this intramolecular process. Large polarization at the TSs promoted by hydrogen-bonds and implicit solvation by water together with a high electrophilicity-nucleophilicity difference consistently explains the catalytic effects of water molecules.

Idioma originalInglés
Páginas (desde-hasta)13687-13703
Número de páginas17
PublicaciónMolecules
Volumen17
N.º11
DOI
EstadoPublicada - nov. 2012

Áreas temáticas de ASJC Scopus

  • Química analítica
  • Química (miscelánea)
  • Medicina molecular
  • Ciencias farmacéuticas
  • Descubrimiento de medicamentos
  • Química física y teórica
  • Química orgánica

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