Artículos de revistas
On the catalytic effect of water in the intramolecular diels-alder reaction of quinone systems: A theoretical study
Fecha
2012Registro en:
Molecules, Volumen 17, Issue 11, 2018, Pages 13687-13703
14203049
10.3390/molecules171113687
Autor
Soto Delgado, Jorge
Aizman, Arie
Contreras Ramos, Renato
Domingo, Luis R.
Institución
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 intramolec