An ONIOM study on the enantioselective Diels-Alder reaction catalyzed by SiO2 - Immobilized chiral oxazaborolidinium cation

Omar, N.Y.M. and Rahman, N.A. and Zain, S.M. (2010) An ONIOM study on the enantioselective Diels-Alder reaction catalyzed by SiO2 - Immobilized chiral oxazaborolidinium cation. Journal of Molecular Catalysis A: Chemical, 333 (1-2). pp. 145-157. ISSN 1381-1169

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Abstract

The mechanism and enantioselectivity of the Diels-Alder reaction between 2-methyl-1,3-butadiene and 2,3-dimethyl-1,4-benzoquinone catalyzed by SiO2-supported chiral cationic oxazaborolidinium catalyst were investigated by the hybrid ONIOM(B3LYP/6-31G(d):UFF) method. The amorphous silica bulk was obtained by classical molecular dynamics using the melt-quench method and the heterogeneous surface was created by cleaving the bulk structure. The resultant amorphous silica surface was found to closely resemble silicas thermally treated at 673 K. The organocatalytic Diels-Alder reaction on the silica surface was observed to proceed via a concerted but highly asynchronous mechanism. The preferred transition state was found to correspond to an endo arrangement of the diene and the catalyst-coordinated benzoquinone, and the enantioselectivity was calculated to be 86.5% at 298 K. The mechanism and enantioselectivity of the studied reaction were generally comparable to those observed for the homogeneous catalyst. (C) 2010 Elsevier B.V. All rights reserved.

Item Type: Article
Uncontrolled Keywords: Density functional theory; ONIOM; Heterogeneous catalysis; Enantioselective Diels-Alder reaction; Asynchronous concerted mechanism
Subjects: Q Science > Q Science (General)
Depositing User: Mr Faizal 2
Date Deposited: 12 Jan 2015 04:05
Last Modified: 25 May 2017 08:41
URI: http://eprints.um.edu.my/id/eprint/11881

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