Catalytic Asymmetric Dehydrogenative Si-H/N-H Coupling: Synthesis of Silicon-Stereogenic Silazanes.

Abstract

Despite growing progress in the construction of silazanes, the catalytic asymmetric synthesis of silicon-stereogenic silazanes is significantly less explored and remains a considerable challenge. Herein, we report a highly enantioselective synthesis of silicon-stereogenic silazanes via catalytic dehydrogenative coupling of dihydrosilanes with anilines. The reaction readily produces a wide range of chiral silazanes and bis-silazanes in excellent yields and stereoselectivities (up to 99% ee). Further utility of this process is demonstrated by the construction of polycarbosilazanes featuring configurational main chain silicon-stereogenic chirality. In addition, the straightforward transformation of the enantioenriched silazanes delivers various chiral silane compounds in a stereospecific fashion, illustrating their potential utilities as synthons for the synthesis of novel silicon-containing functional molecules.