Nickel‐Catalyzed Reductive C(sp2)−Si Coupling of Chlorohydrosilanes via Si−Cl Cleavage

Abstract We report here a new method for the synthesis of organohydrosilanes from phenols and ketones. This method is established through reductive C−Si coupling of chlorohydrosilanes via unconventional Si−Cl cleavage. The reaction offers access to aryl‐ and alkenylhydrosilanes with a scope that is complementary to those of the established methods. Electron‐rich, electron‐poor, and ortho ‐/ meta ‐/ para ‐substituted (hetero)aryl electrophiles, as well as cyclic and acyclic alkenyl electrophiles, were coupled successfully. Functionalities, including Grignard‐sensitive groups (e.g., primary amine, amide, phenol, ketone, ester, and free indole), acid‐sensitive groups (e.g., ketal and THP protection), alkyl‐Cl, pyridine, furan, thiophene, Ar‐Bpin, and Ar‐SiMe 3 , were tolerated. Gram‐scale reaction, incorporation of ‐Si(H)R 2 into complex biologically active molecules, and derivatization of formed organohydrosilanes are demonstrated.