Photo‐ or Electrochemical N‐P Cross ‐Hetero‐Dehydrogenative Couplings between Amines and Phosphonothioates

Abstract We present two distinct synthetic approaches for the synthesis of diversely functionalized thiophosphoramidates, employing either photochemical or electrochemical strategies via N−P cross ‐hetero‐dehydrogenative coupling. Both methods provide a practical and efficient route to access this significant class of biologically relevant thiophosphoramidates. Key advantages of the protocol include mild reaction conditions, the use of visible light and electrochemical cells as sustainable tools, and energy efficiency enabled by a low‐energy visible light source and low‐current operation. Furthermore, the process utilizes low‐cost substrates and a nontoxic photosensitizer, delivers high yields, exhibits broad substrate scope with excellent functional group tolerance, and offers operational simplicity with a strong emphasis on eco‐friendliness.