Metallaphotoredox-Enabled Construction of the P(O)-N Bond from Aromatic Amines and P(O)-H Compounds.

We have developed a dual copper/photoredox-catalyzed approach for the construction of the P(O)-N bond from commercially available aromatic amines and P(O)-H compounds. This metallaphotoredox method avoids toxic or corrosive reagents and does not require prefunctionalized substrates. The reaction has a broad substrate scope and is suitable for the synthesis of phosphonamides and phosphinamides, thus complementing the previous nonphotochemical approaches. The reaction is amenable to the direct modification of drug molecules and can be conducted on a gram scale.