Recent progress in metal-catalyzed C(sp3)-P bond formation

The construction of C(sp3)-P bonds is of paramount importance in organic synthesis, catalysis, and materials science. Organophosphorus compounds containing C(sp3)-P bonds serve as pivotal structural motifs in ligands, pharmaceuticals, agrochemicals, and functional materials. While traditional methods for C(sp3)-P bond formation largely rely on nucleophilic substitution or coupling of reactive organometallic reagents, recent years have witnessed significant advancements in metal-catalyzed approaches. This review highlights the recent developments in C(sp3)-P bond formation enabled by metals including Cu, Fe, Bi, Pd, Ni, Ru, Rh, and Co, with particular emphasis on methodologies that activate simple C(sp3)-H bonds or utilize readily available chemical feedstocks. Key mechanistic paradigms, including photoredox/transition metal dual catalysis, metal-catalyzed radical processes, and photo-induced ligand-to-metal charge transfer (LMCT), are critically discussed. This review evaluates the mechanistic insights, applications, and limitations of these methodologies in the synthesis of organophosphorus compounds, and provides perspectives on future directions to promote further advancements in C(sp3)-P bond formation strategies.