Merging Photocatalysis with Chiral Lewis Acid Catalysis for Enantioselective Hydrosilylation/Hydrogermylation of Electron‐Deficient Alkenes

Abstract Organosilicon compounds demonstrate widespread applications in many fields. Transition‐metal‐catalyzed asymmetric hydrosilylation represents one of the most common and effective methods to synthesize chiral organosilicon compounds, but it largely relies on electron‐rich alkenes and structurally specific hydrosilanes. Visible light photocatalysis has emerged as a promising new platform for hydrosilylation. However, the enantiocontrol of photoinduced asymmetric hydrosilylation concerning highly reactive radical species is a great challenge. Herein, we report a synergistic catalytic strategy for enantioselective hydrosilylation of electron‐deficient alkenes by merging anthraquinone as a dual‐tasked photocatalyst with a chiral Lewis acid catalyst. This protocol shows broad hydrosilane scope with efficient chemo‐, regio‐ and enantioselectivities, delivering diverse enantioenriched organosilicon compounds, which could be readily converted into a series of medicine molecules. Mechanistic studies reveal that the π–π interaction between the photocatalyst and the alkene is crucial for enantiocontrol. Additionally, enantioselective radical hydrogermylation was also achieved under the visible light photoinduced synergistic catalysis.