期刊
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY
卷 -, 期 4, 页码 529-541出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/ejic.200900961
关键词
Density functional calculations; Mechanistic studies; Asymmetric catalysis; Hydrosilylation; Copper
资金
- Centre National de la Recherche Scientifique (CNRS)
- Ministers de I'Education Nationale, de la Recherche et de la Technologic
- Action Concertee Incitative (ACI)
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.
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