Two-in-one metallaphotoredox cross-couplings enabled by a photoactive ligand

Prized for their ability to streamline organic synthesis, cross-couplings have become fundamental reactions in many settings. In photoinduced cross-coupling chemistry, metallaphotoredox catalysis remains state-of-the-art, typically featuring a dual catalytic partnership of a chromophoric compound and an organometallic complex. However, designing such a highly variable, multicomponent linchpin ranks among the most challenging endeavors in synthetic practice since identifying the optimal combination often requires considerable experimentation. Herein, we outline a simple and general solution to this problem by devising a photoactive ligand that could complex with a series of transition metals and serve as “two-in-one” metallaphotoredox catalysts. Our bifunctional system is compatible with a diverse pool of nucleophilic and electrophilic coupling partners and highly enabling in visible-light-driven C–C and C–X bond formations. We envision that this nonclassical toolkit would open chemical space for novel coupling reactivities and inspiring future research efforts in a broad scientific community.