Copper-Catalyzed Vicinal Cyano-, Thiocyano-, and Chlorophosphorylation of Alkynes: A Phosphinoyl Radical-Initiated Approach for Difunctionalized Alkenes

A copper-catalyzed difunctional cyano-, thiocyano-, and chlorophosphorylation reaction of alkynes with P­(O)–H compounds and coupling partners (TBACN, TMSNCS, TMSCl) is described. The reaction introduces versatile groups (−P­(O)­R2 and −CN, −SCN, or −Cl) to form tri- and tetrasubstituted alkenyl phosphine oxides/phosphonates regio- and stereoselectively.