Insertion of Arynes into Arylphosphoryl Amide Bonds: One-Step Simultaneous Construction of C–N and C–P Bonds

The insertion of arynes into arylphosphoryl amide bonds to synchronously construct C–P and C–N bonds is described. Arynes generated in situ from o-triflate arylsilanes under fluoride-promoted conditions insert into relatively inert P–N bonds, producing o-amine-substituted arylphosphine oxides. This process provides a simple pathway for the preparation of precursors for a number of bidentate aminophosphine ligands.