Dehydrogenative α,γ-Diphosphinylation of Allylamines Enabled by Photoinduced Cobaloxime Catalysis

A regioselective radical α,γ-diphosphinylation of allylamines with secondary phosphine oxides by photoinduced cobaloxime catalysis is described. The reaction tolerates a wide range of allylamines and phosphine oxides, affording α-amino diphosphine dioxides in moderate to good yields with hydrogen evolution. The synthesis of new diphosphine monoxide and diphosphine ligands and the promising antitumor activities of products demonstrate the great potential applications of this approach in catalysis and drug discovery. The detailed mechanism studies indicate that this reaction likely proceeds through a dehydrogenative allylic phosphinylation and nucleophilic addition process.