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

Despite growing progress in the construction of silazanes,thecatalytic asymmetric synthesis of silicon-stereogenic silazanes issignificantly less explored and remains a considerable challenge.Herein, we report a highly enantioselective synthesis of silicon-stereogenicsilazanes via catalytic dehydrogenative coupling of dihydrosilaneswith anilines. The reaction readily produces a wide range of chiralsilazanes and bis-silazanes in excellent yields and stereoselectivities(up to 99% ee). Further utility of this process isdemonstrated by the construction of polycarbosilazanes featuring configurationalmain chain silicon-stereogenic chirality. In addition, the straightforwardtransformation of the enantioenriched silazanes delivers various chiralsilane compounds in a stereospecific fashion, illustrating their potentialutilities as synthons for the synthesis of novel silicon-containingfunctional molecules.

Automated summary

In this study, a highly enantioselective synthesis of silicon-stereogenic silazanes was achieved through catalytic dehydrogenative coupling of dihydrosilanes with anilines. The reaction synthesized various chiral silazanes and bis-silazanes with excellent yields and stereoselectivities (up to 99% ee). Further applications included the construction of polycarbosilazanes with configurational main chain silicon-stereogenic chirality, and the transformation of the enantioenriched silazanes into various chiral silane compounds, demonstrating their potential utilities as synthons for novel silicon-containing functional molecules.