Highly Regio‐, Stereo‐, and Enantioselective Copper‐Catalyzed B−H Bond Insertion of α‐Silylcarbenes: Efficient Access to Chiral Allylic gem‐Silylboranes

Herein, we report the development of a method for highly regio-, stereo-, and enantioselective B-H bond insertion reactions of α-silylcarbenes generated from 1-silylcyclopropenes in the presence of a chiral copper(I)/bisoxazoline catalyst for the construction of chiral γ,γ-disubstituted allylic gem-silylboranes, which cannot be prepared by any other known methods. This reaction is the first highly enantioselective carbene insertion reaction of α-silylcarbenes ever to be reported. The method shows general applicability for various 3,3-disubstituted silylcyclopropenes and exclusively affords E-products. The novel chiral γ,γ-disubstituted allylic gem-silylborane products are versatile allylic bimetallic reagents with high stability and have great synthetic potential, especially for the construction of complex molecules with continuous chiral centers.