Nickel/Photoredox Dual‐Catalyzed Migratory Reductive C( <i>sp</i> ² )–H/Si–Cl Cross‐Coupling

ABSTRACT Organosilicon compounds have been extensively utilized in both industry and academia. Transition metal‐catalyzed migratory cross‐coupling involving 1, n ‐metal migration allows functionalization of C−H bonds on a remote site that are otherwise difficult to achieve. However, until now, forging C−Si bond via migratory cross‐coupling seems to have not been presented. Herein, we report a nickel/photoredox dual‐catalyzed migratory cross‐coupling that enables the first formal remote C( sp 2 )–H silylation with chlorosilanes, thus achieving site‐selective ipso / ortho ‐difunctionalization of readily available aryl bromides. The protocol proceeds under visible‐light irradiation without stoichiometric metallic reductants and delivers a broad array of multisubstituted arylsilanes with excellent chemo‐, regio‐, and E / Z ‐selectivity. The synthetic utility of the method is further demonstrated through diverse downstream transformations and the preparation of silicon‐containing polymers, highlighting its potential in complex molecule synthesis and materials chemistry.