A series of aryl-based chiral NCN′ pincer palladium-(II) complexes 4a−k were synthesized via C−H activation of the (pyridyl)-(imidazolinyl)benzene ligands, which proceeded smoothly with PdCl 2 as the palladium source in the presence of Et 3 N or NaHCO 3 base in toluene under reflux. All of the complexes have been characterized by elemental analysis and 1 H and 13 C{ 1 H} NMR spectroscopy. In addition, the molecular structures of complexes 4a, 4c, and 4f have been determined by X-ray singlecrystal diffraction analysis. The obtained chiral Pd pincers were applied to catalytic asymmetric reactions of acrylonitrile and dichloroacetonitrile with sulfonimines. With a catalyst loading of 5 mol % and the assistance of AgOAc, these complexes acted as active but moderately stereoselective catalysts for the aforementioned reactions.
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