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

Prized for their ability to streamline organic synthesis, cross -cou-plings have become fundamental reactions in many settings. In photoinduced cross-coupling chemistry, metallaphotoredox catal-ysis remains state-of-the-art, typically featuring a dual catalytic part-nership of a chromophoric compound and an organometallic com-plex. 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 gen-eral solution to this problem by devising a photoactive ligand that could complex with a series of transition metals and serve as two-in-onemetallaphotoredox 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.

Automated summary

Cross-coupling reactions are highly valued for their ability to improve organic synthesis efficiency. This study presents a simple and versatile solution to the design of multicomponent complexes, by developing a photoactive ligand that can serve as a bifunctional metallaphotoredox catalyst. The system is compatible with various nucleophilic and electrophilic coupling reactions and enables visible-light-driven bond formations. This nonclassical toolkit is expected to open up chemical space for novel coupling reactions and inspire future research efforts.