Theoretical insights into the enantioselectivity and mechanism of diels-alder reactions involving chiral cationic oxazaborolidinium catalyst
Document Type
Article
Publication Date
1-1-2011
Abstract
The chiral oxazaborolidinium ion catalyzed Diels-Alder reaction between 2-methyl-1,3-butadiene and 2,3-dimethyl-1,4-benzoquinone was studied by means of density functional theory (DFT) at the B3LYP/6-31G(d) level of theory. Different DFT-based theoretical approaches including the reaction force, the natural population analysis of the charge transfer, the topological analysis of the electron localization function (ELF), and the global and local reactivity indices were applied to investigate and rationalize the mechanism and the endo/exo selectivity of this reaction. The changes in the physical and chemical properties of the reacting molecules along the intrinsic reaction coordinate (IRC) were also monitored to shed light on the mechanistic details. The analysis of the studied Diels-Alder reaction within the framework of DFT revealed and explained the preference of the endo path to the exo channel, and pointed out a concerted but highly asynchronous reaction mechanism. © 2011 The Chemical Society of Japan.
Keywords
B3LYP/6-31G, Benzoquinones, Diels-Alder reaction, Electron localization function, Intrinsic reaction coordinate, Natural population analysis, Physical and chemical properties, Reaction forces, Reaction mechanism, Reactivity indices, Theoretical approach, Topological analysis, Butadiene, Charge transfer, Chemical properties, Enantioselectivity, Ion exchange, Density functional theory
Divisions
CHEMISTRY
Publication Title
Bulletin of the Chemical Society of Japan
Volume
84
Issue
2
Additional Information
Department of Chemistry, Faculty of Science Building, University of Malaya, 50603 Kuala Lumpur, MALAYSIA