Visible‐Light‐Induced C(sp²)─P Cross‐Coupling Reactions Catalyzed by Boron Carbonitride

Abstract A visible‐light‐induced protocol has been developed for the construction of C(sp 2 )─P bonds with heterogeneous boron carbonitrides (BCN). The system features with broad scope and mild reaction conditions, providing various aryl phosphates in moderate to good yields from arenes and aryl halides. Mechanism studies verify a radical process, and C─H bond cleavage is not involved in the rate‐determined step. Furthermore, the strategy allows the late‐stage phosphonation of biologically active compounds and facilitates gram‐scale synthesis, which offers a metal‐free arene for valuable phosphorus‐containing compounds.