H₈-BINOL-derived phosphine-oxazolines complexed with iridium were successfully applied for the asymmetric hydrogenation of the carbon-carbon double bond of exocyclic α,β-unsaturated carbonyl compounds. A valuable series of α-chiral cyclic ketones, lactones, and lactams were therefore provided via the reaction in high yields and good to excellent enantioselectivity of up to 95 % ee. The effects of the ligands and substrate structures on the asymmetric catalysis were also discussed.

A valuable class of new heterocyclic and alicyclic prochiral α-aminomethylacrylates has been conveniently synthesized through a three-step transformation involving a Baylis–Hillman reaction, O-acetylation, and a subsequent allylic amination. The corresponding novel β²-amino acid derivatives were prepared with excellent enantioselectivities and high yields by catalytic asymmetric hydrogenation using the catalyst rhodium(Et-Duphos) (Et-Duphos=2′,5′,2′′,5′′-tetraethyl-1,2-bis(phospholanyl)benzene)) under mild reaction conditions (up to 99 % ee and S/C=1000). The influence of the substrate on the enantioselectivity and reactivity is investigated, and the most suitable substrate configuration for the highly efficient enantioselective hydrogenation of β-substituted α-aminomethylacrylates under the Rh–Duphos system is reported. The current protocol provides a very practical, facile, and scalable method for the preparation of heterocyclic and alicyclic β²-amino acids and their derivatives.

Three novel atropisomeric bridged P,N-ligands were prepared using a highly efficient central-to-axial transfer strategy as the protocol. The new chiral ligands were successfully applied in the palladium-catalyzed asymmetric Suzuki–Miyaura coupling reaction, Up to 98% yield and 82% ee were obtained in the enantioselective synthesis of axially chiral biarylphosphonates.

A new strategy was developed for the synthesis of a valuable class of α-aminomethylacrylates via the Baylis–Hillman reaction of different aldehydes with methyl acrylate followed by acetylation of the resulting allylic alcohols and S_N2′-type amination of the allylic acetates. Asymmetric hydrogenation of these diverse olefinic precursors using rhodium(Et-Duphos) catalysts provided the corresponding β²-amino acid derivatives with excellent enantioselectivities and exceedingly high reactivities (up to >99.5% ee and S/C=10,000). The first hydrogenation of (Z)-configurated substrates was studied for the synthesis of β²-amino acid derivatives. The high influence of the substrate geometry and steric hindrance on the reactivity and enantioselectivity was also disclosed for this reaction. This protocol provides a highly practical, facile and scalable method for the preparation of optically pure β²-amino acids and their derivatives under mild reaction conditions.