Premium
Mechanistic Studies on the Copper‐Catalyzed Hydrosilylation of Ketones
Author(s) -
Issenhuth JeanThomas,
Notter FrançoisPaul,
Dagorne Samuel,
Dedieu Alain,
BelleminLaponnaz Stéphane
Publication year - 2010
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200900961
Subject(s) - chemistry , hydrosilylation , ketone , enantiopure drug , copper , silyl ether , catalysis , catalytic cycle , alkoxy group , kinetic isotope effect , phosphonium , dimer , reactivity (psychology) , silane , kinetic resolution , isotopic labeling , medicinal chemistry , organic chemistry , silylation , enantioselective synthesis , deuterium , medicine , alkyl , physics , alternative medicine , quantum mechanics , pathology
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.