Fiche publication
Date publication
février 2010
Auteurs
Membres identifiés du Cancéropôle Est :
Dr BELLEMIN-LAPONNAZ Stéphane
Tous les auteurs :
Issenhuth JT, Notter FP, Dagorne S, Dedieu A, Bellemin-Laponnaz S
Résumé
The copper-catalyzed asymmetric hydrosilylation of ketones is an efficient method for the synthesis of chiral enantiopure secondary alcohols. Herein, we present a detailed computational study (DFT/B3LYP) of the copper(I) -catalyzed reaction. In particular, the two transition states involved in the catalytic cycle have been determined. The insertion of the ketone into the Cu-H bond was found to have a lower activation barrier than the reaction of the copper alkoxy intermediate with the silane, which regenerates Cu-H along with the silyl ether product. Our findings also reveal the importance of the copper hydride dimer in controlling the reactivity toward the ketone. The conclusions are supported by experimental mechanistic investigations including kinetic studies, kinetic isotope effect, and isotope labeling measurements.
Référence
Eur J Inorg Chem. 2010 Feb;4:529-41.
