Copper-Catalyzed Stereoselective Cyanation/Phosphorylation of Formamides with TMSCN and P(O)–H Bonds

A novel copper-catalyzed approach for the stereoselective cyanation and phosphorylation of formamides has been developed. This protocol enables the direct conversion of a broad range of formamides and phosphorylation agents, including H-phosphonates, H-phosphinates, and H-phosphine oxides, into the target cyanation/phosphorylation products with good to excellent yields. Notably, when optically active H-phosphinates are employed, the transformation exhibits exceptional stereoselectivity. In combination with DFT calculation and systematic step-by-step control experiments, a possible reaction mechanism is proposed.