Chiral (phosphine)-(imidazoline) PCN pincer palladium(II) complexes: synthesis and application in asymmetric hydrophosphination of 2-alkenoylpyridines with diphenylphosphine

A series of new chiral PCN pincer Pd(II) complexes 3a-l with aryl-based (phosphine) (imidazoline) ligands were conveniently synthesized from readily available starting materials with the key step being phosphination/C-H palladation reaction. All of the new complexes were characterized by H-1 NMR, C-13{H-1) NMR, P-31 {H-1) NMR, and elemental analysis. In addition, the molecular structures of complexes 3c, 3e, 3i, and 3k have been determined by X-ray single crystal diffraction analysis. The potential of the obtained pincer Pd (II) complexes in catalytic enantioselective hydrophosphination reaction was examined. With a loading of 5 mol% and in the presence of a KOAc base, complex 3e acted as an active and stereoselective catalyst for hydrophosphination of various 2-alkenoylpyridines with diphenylphosphine, providing optically active pyridine-containing phosphine derivatives with structural diversity in excellent yields with moderate to good enantioselectivities (up to >99 yield and 87% ee).