Nitrogen-Assisted Ortho Lithiation: One-Pot Synthesis of New Classes of Bidentate and Tetradentate Mixed P∼N Ligands

Metalation of one aryl group of Ph3PNR (R = methyl, isopropyl) affords an easy access to the corresponding lithium salt, which in turn reacts with chlorophosphines R2PCl (R = Ph, i-Pr) to yield a new class of bidentate ligand featuring one iminophosphorane and one phosphino group. Reaction of the phenyl derivative with [Pd(COD)Cl2] yielded the expected six-membered palladacycle complex, which was structurally characterized. Extension of this new synthetic methodology toward the elaboration of enantiomerically pure tetradentate ligands has also been achieved.