Speciation and Mechanistic Studies of Chiral Copper(I) Schiff Base Precursors Mediating Asymmetric Carbenoid Insertion Reactions of Diazoacetates into the Si-H Bond of Silanes
The speciation and mechanistic activities of chiral copper(I) Schiff base precursors, mediating asymmetric carbenoid insertion reactions of diazoacetates into the Si-H bond of silanes, are studied. Mechanistic analysis of the [(R,R-1)CuI(CH3CN)]+-mediated asymmetric insertion of the carbenoid precursor PhC(N2)CO2Me into the Si-H bonds of silanes (R,R-1 is a chiral diimine ligand) indicates, that despite structural complexity, the reaction is mediated by a mononuclear and apparently highly preorganized copper-carbene moiety, which performs concerted insertion of the carbenoid carbon into a weakly polarized Si-H bond, the latter entering hydrogen-first from the open side of the C2-symmetric activity.
L. A. Dakin et al., "Speciation and Mechanistic Studies of Chiral Copper(I) Schiff Base Precursors Mediating Asymmetric Carbenoid Insertion Reactions of Diazoacetates into the Si-H Bond of Silanes," Organometallics, American Chemical Society (ACS), Jan 2000.
The definitive version is available at http://dx.doi.org/10.1021/om0003786
Article - Journal
© 2000 American Chemical Society (ACS), All rights reserved.