Addition of a Cyclophosphine to Nitriles: An Inorganic Click Reaction Featuring Protio, Organo, and Main-Group Catalysis

The addition of a cyclotriphosphine to a broad range of nitriles gives access to the first examples of free 1-aza-2,3,4-triphospholenes in a rapid, ambient temperature, one-pot, high-yield protocol. The reaction produces electron-rich heterocycles (four lone pairs) and features homoatomic σ-bond heterolysis, thereby combining the key features of the 1,3-dipolar cycloaddition chemistry of azides and cyclopropanes. Also reported is the first catalytic addition of P-P bonds to the C≡N bond. The coordination chemistry of the new heterocycles is explored.