Title

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

Abstract

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.

Department(s)

Chemistry

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2000 American Chemical Society (ACS), All rights reserved.


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