Enantioselectivity Induced by Oxazaborolidine Supported on Mesoporous Silica or by Its Analog in Homogeneous Phase.docVIP

Molecules 2010, 15, 3643-3660; doi:10.3390/moleculeOPEN ACCESS molecules ISSN 1420-3049 /journal/molecules Article Enantioselectivity Induced by Oxazaborolidine Supported on Mesoporous Silica or by Its Analog in Homogeneous Phase Jeremy H. Yune, Fran?oise Quignard and Karine Molvinger * Institut Charles Gerhardt Montpellier, UMR 5253 CNRS/ENSCM/UM2/UM1, Matériaux Avancés pour la Catalyse et la Santé, ? MACS ? - 8, rue de l’Ecole Normale, 34296 Montpellier cedex 5, France * Author to whom correspondence should be addressed; E-Mail: karine.molvinger@enscm.fr. Received: 19 April 2010; in revised form: 6 May 2010 / Accepted: 12 May 2010 / Published: 18 May 2010 Abstract: The impact of immobilization of oxazaborolidines supported on silica via different substituents on the boron and nitrogen atoms is evaluated in the enantioselective reduction of acetophenone. The performances of the homogeneous analog oxazaborolidines and silica-supported ones are compared by varying different parameters. This article deals with the synthesis, characterization and catalytic evaluation of silica- supported oxazaborolidines, their recycling capabilities and regeneration limitations. Keywords: oxazaborolidine; supported catalyst; mesoporous silica; asymmetric reduction of acetophenone 1. Introduction Since their discovery by Itsuno et al. in 1981 [1] and their major development by Corey et al., chiral 1,3,2-oxazaborolidines have proven to be highly effective homogeneous catalysts for the enantioselective reduction of ketones to chiral secondary alcohols by borane. The mechanism has been elucidated by Corey et al. [2]: in fact the oxazaborolidine (synthesized from an amino alcohol) forms a complex with the borane and this complex rapidly reduces the ketones with excellent yields and enantiomeric excesses. Excellent results have been reported by Quallich using (1S,2R)-2-amino-1,2- diphenylethanol, since one