Cobalt-Catalyzed Oxidative C(sp3)-H Phosphonylation for α-Aminophosphonates via C(sp3)-H/P(O)-H Coupling.

The first oxidative C(sp3)-H phosphonylation of tertiary aliphatic amines has been developed. The use of cobalt acetate as a catalyst, N-hydroxyphthalimide as a cocatalyst, and air as an oxidant enabled the conversion of tertiary aromatic and aliphatic amines into α-aminophosphonates in moderate to excellent yields under mild conditions via a cross dehydrogenative coupling reaction.