A direct enantioselective C-acylation of 3-substituted benzofuran-2(3H)-ones (with up to 97% ee) was developed using a chiral bicyclic imidazole catalyst OAc-DPI and an achiral tertiary amine additive DIPEA. The reaction mechanism for the direct C-acylation has been investigated using both experimental and theoretical studies.

Chiral organophosphorus compounds possessing a P-stereogenic center have been widely used as agricultural chemicals, pharmaceuticals, organocatalysts, and ligands for transition-metal catalysis. P-Stereogenic intermediates bearing a tert-butyl(methyl)phosphino group are important for the preparation of several commonly used diphosphine ligands. However, previously reported synthetic methods used hazardous starting materials and are difficult to operate. In order to overcome these limitations, a new and convenient synthesis for a number of P-stereogenic intermediates possessing a tert-butyl(methyl)phosphino group has been developed. The reported route relies on an air- and moisture-stable secondary phosphine oxide prepared from a readily available starting material, trichlorophosphane.

Via a strategy of asymmetric reductive desymmetrization, chiral cis-epoxy naphthoquinols with multiple contiguous stereocenters and functional groups were synthesized with excellent enantioselectivities (96–99% ee) and diastereoselectivities (8/1–15/1). A combined asymmetric hydrogenation/transfer hydrogenation mechanism was proposed based on experimental results.

Catalyzed by a rhodium complex of P-stereogenic diphosphine ligand (R)-2-tert-butylmethylphosphino-3-(di-tert-butylphosphino)quinoxaline ((R)-3H-QuinoxP*), five-membered cyclic α-dehydroamino ketones bearing endocyclic vinyl and endocyclic keto-carbonyl groups were sequentially hydrogenated to give chiral cyclic trans-β-amino alcohols with two contiguous stereocenters in quantitative conversions, excellent enantioselectivities and good diastereoselectivities.

Catalyzed by a rhodium complex of P-stereogenic diphosphine ligand trichickenfootphos (TCFP), asymmetric hydrogenation of racemic aldimines via dynamic kinetic resolution has been realized for the preparation of chiral arylglycines with good yields and enantioselectivities.

A direct enantioselective C-acylation of 3-substituted benzofuran-2(3H)-ones (with up to 97% ee) was developed using a chiral bicyclic imidazole catalyst OAc-DPI and an achiral tertiary amine additive DIPEA. The reaction mechanism for the direct C-acylation has been investigated using both experimental and theoretical studies.