Selective P−C(sp3) Bond Cleavage and Radical Alkynylation of α‐Phosphorus Alcohols by Photoredox Catalysis

Abstract Herein the first P−C(sp 3 ) bond cleavage and radical alkynylation of α ‐phosphorus alcohols to construct phosphonoalkynes is reported. The phosphorus radical is generated upon P−C bond cleavage reaction via the alkoxyl radical through photoredox catalysis with cyclic iodine(III) reagents. Various arylphosphinoyl‐, alkylphosphinoyl‐, phosphonate‐, and phosphonic amide alcohols serve as radical phosphorus precursors to construct phosphonoalkynes for the first time.