Asymmetric CuI-Catalyzed Insertion Reaction of 1-Aryl-2,2,2-trifluoro-1-diazoethanes into Si-H Bonds.

Abstract

An asymmetric copper(I)-catalyzed Si-H insertion reaction of 1-aryl-2,2,2-trifluoro-1-diazoethanes in dimethyl carbonate as a green solvent alternative was developed. A C2-symmetric copper(I) diimine complex enabled the asymmetric insertion reaction to give enantioenriched (1-aryl-2,2,2-trifluoroethyl)silanes with excellent stereoselectivities (up to 98:2 er). Successful conversion of the silanes into the corresponding alcohols was performed with retention of stereochemistry. Mechanistic studies and DFT calculations support the proposed model for the observed stereoselectivities.