Tf2O-Mediated P(O)-N Bond Formation of Either P(O)-OH or P(O)-H Reagents with Multitype Amines.

We have developed a Tf2O-mediated approach for the direct amination of either P(O)-OH or P(O)-H reagents with a variety of aliphatic or aromatic amines. Without the requirement of precious metals and toxic reagents, this protocol provides an alternative route to various phosphinamides and phosphoramides. The reaction proceeds under simple and mild conditions and can be effectively scaled up with similar efficiency.

Tf2O/DMSO-mediated dual activation of aryl phosphinate to access various aryl phosphonates.

A metal-free method for the dual activation of aryl phosphinate has been developed; the P-H and P-O bonds are sequentially activated by the Tf2O/DMSO system. Without the requirement of metals and unstable P-reagents, this one-pot procedure provides a convenient and practical access to a variety of aryl phosphonates. A mechanism involving twice generation of electrophilic P-species and two SN-processes is proposed on the basis of the control experiments.

Bisphosphorylation of anhydrides - convenient access to bisphosphonates with a P-O-C-P motif.

A novel strategy of bisphosphorylation of anhydrides with P(O)-H reagents via a DMAP-catalyzed and DBU-promoted process has been developed. These one-step transformations proceed efficiently to provide convenient access to a variety of P-O-C-P motif containing organophosphorus compounds. In addition, the gram-scale synthesis and the efficient recovery of the by-product highlight the sustainability and applicability of this method.