Visible-Light-Induced, Metal-Free Carbene Insertion into B–H Bonds between Acylsilanes and Pinacolborane

Abstract

Carbene insertion reactions with B-H bonds are a challenging but promising method for the synthesis of organoboranes. Herein, we report visible-light-induced B-H insertions of HBpin with acylsilane. This metal-free and operationally simple reaction proceeds in an atom-economical way with broad substrate scope under mild reaction conditions, affording a variety of important α-alkoxyorganoboronate esters in quantitative yields. Control experiments and density functional theory calculations suggest that the siloxycarbene generation from the T₁ state of acylsilane and the carbene insertion into the B-H bond occurred in a concerted manner.