A series of easy-to-prepare and modular chiral ,-bidentate phosphoramidites were synthesized. With respect to Pd(II), these ligands showed the ability to form stable ,-chelate allylic complexes. The structures of the ligands and their complexes were confirmed by 2D NMR spectroscopy and single-crystal X-ray diffraction. These chiral inducers provided up to 99% in the Pd-catalyzed asymmetric allylic substitution of ()-1,3-diphenylallyl acetate with C- and N-nucleophiles and up to 94% in the Pd-mediated allylic alkylation of cinnamyl esters with β-ketoesters and 2,5-dimethylpyrrole. Furthermore, up to 92% with quantitative conversion and chemo- and regioselectivity was achieved in the rare reaction between 2-(diethoxyphosphoryl)-1-phenylallyl acetate and aniline. The effects of the structural parameters, reaction conditions and ligand-to-metal ratio on the catalytic results are discussed. It was shown that the ligands surpass their analogues with different denticity.
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