A series of new chiral phosphine-phosphoramidite ligands with a 3,3'-substituted binaphthyl moiety were prepared from 1-phenylethylamine, and successfully applied in the Rh-catalyzed asymmetric hydrogenation of beta-(acylamino)-acrylates. The research disclosed that the substituents on the 3,3'-positions of binaphthyl moiety significantly influenced the enantioselectivity.

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Readily Available Chiral Phosphine-Aminophosphine Ligands Derived from 1-Phenylethylamine for Rh-Catalyzed Enantioselective Hydrogenations. -Among the novel phosphineaminophosphine derivatives prepared, effective ligands are identified for the Rh-catalyzed asymmetric hydrogenation of enamides (II), Z-β-dehydroamino acid esters (VI), and itaconate (IX). Optimization of the ligand structure is given for each type of substrate. The ligands are not suitable for α-dehydroamino acid esters like (XI). -(ZHOU, X.-M.; HUANG, J.-D.; LUO, L.-B.; ZHANG, C.-L.; ZHENG, Z.; HU*, X.-P.; Tetrahedron: Asymmetry 21 (2010) 4, 420-424,

Highly Enantioselective Rh-Catalyzed Hydrogenation of β-(Acylamino)acrylates: Significant Effect of Substituents on 3,3'-Positions of Binaphthyl Moiety. -Introduction of phenyl substituents at the phosphoramidite backbone of PEAPhos ligand (PEAPP) significantly increases its catalytic activity in the Rh-catalyzed asymmetric hydrogenation of β-(acylamino)acrylates. β-Aryl-β-aminocarboxylates (II) are formed in up to >99% optical purity. -(ZHOU, X.-M.; HUANG, J.-D.; LUO, L.-B.; ZHANG, C.-L.; HU*, X.-P.; ZHENG, Z.; Org.