Lewis Base‐Catalyzed DYKAT of Racemic Chlorohydrosilanes With Grignard Reagents En Route to Si ‐Stereogenic Hydrosilanes

Enantioenriched hydrosilanes bearing a Si ‐stereogenic center have garnered considerable attention due to the relevance in diverse areas of organic chemistry. Their synthesis has predominantly been limited to stereospecific reduction of chiral silylethers or silazanes, or catalytic desymmetrization of prochiral dihydrosilanes. Herein, we disclose a mechanistically distinct strategy: a ( S , R )‐benzotetramisole‐catalyzed dynamic kinetic asymmetric transformation (DYKAT) of racemic chlorohydrosilanes with Grignard reagents. The method enables enantioconvergent Si*─C bond formation, giving Si ‐stereogenic hydrosilanes—many of which are challenging to access via desymmetrization—in high yields and with high enantioselectivity (34 examples, up to 99% yield, 99:1 er ).