Mechanistic Studies on the Copper-Catalyzed Hydrosilylation of Ketones

作者：Issenhuth Jean Thomas; Notter Francois Paul; Dagorne Samuel; Dedieu Alain; Bellemin Laponnaz Stephane^*

来源：European Journal of Inorganic Chemistry, 2010, 2010(4): 529-541.

DOI：10.1002/ejic.200900961

• Density functional calculations
• Mechanistic studies
• Asymmetric catalysis
• Hydrosilylation
• Copper

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.

• 出版日期2010-2