A Visible-Light-Promoted Hydrophosphinylation for C(sp3)–P and C(sp2)–P Bond Construction

A general, efficient visible-light-promoted catalyst-free hydrophosphinylation is reported. This protocol enables direct C(sp3)–P and C(sp2)–P bond construction from readily available R2P(O)–H and various unsaturated substrates under simple and mild visible-light irradiation conditions. The reaction exhibits broad substrate scope and good functional group tolerance, delivering diverse alkylphosphine oxides, alkenylphosphine oxides, and α-aminophosphine oxides in yields up to 92%. The synthetic utility is demonstrated by gram-scale synthesis, late-stage functionalization of complex molecules, and facile derivatization into valuable phosphine ligands and phosphorus-containing bioactive molecules.