Chemoselective Synthesis of α-Amino-α-cyanophosphonates by Reductive Gem-Cyanation-Phosphonylation of Secondary Amides.

A novel approach to α-amino-α-cyanophosphonates has been developed. The method features a Tf2O-mediated reductive geminal cyanation/phosphonylation of secondary amides. Mild reaction conditions, high bond-forming efficiency, inexpensive readily available starting materials, and good to excellent yields with wide functional group compatibility constitute the main advantages of this method. The protocol can be run on a gram scale.