A series of tridentate ferrocene-based amino-phosphine acid (f-Ampha) ligands have been successfully developed. The f-Ampha ligands are extremely air stable and exhibited excellent performance in the Ir-catalyzed asymmetric hydrogenation of ketones (full conversions, up to >99% ee, and 500 000 TON). DFT calculations were performed to elucidate the reaction mechanism and the importance of the -COOH group. Control experiments also revealed that the -COOH group played a key role in this reaction.

A series of modular and rich electronic tridentate ferrocene aminophosphoxazoline ligands (f-amphox) have been successfully developed and used in iridium-catalytic asymmetric hydrogenation of simple ketones to afford corresponding enantiomerically enriched alcohols under mild conditions with superb activities and excellent enantioselectivities (up to 1 000 000 TON, almost all products up to >99% ee, full conversion). The resulting chiral alcohols and their derivatives are important intermediates in pharmaceuticals.

We have successfully developed a series of novel and modular ferrorence-based amino-phosphine-alcohol (f-Amphol) ligands, and applied them to iridium-catalyzed asymmetric hydrogenation of various simple ketones to afford the corresponding chiral alcohols with excellent enantioselectivities and conversions (98-99.9 % ee, >99 % conversion, turnover number up to 200 000). Control experiments and density functional theory (DFT) calculations have shown that the hydroxyl group of our f-Amphol ligands played a key role in this asymmetric hydrogenation.

Iridium-catalyzed asymmetric hydrogenation of prochiral halogenated ketones was successfully developed to prepare various chiral halohydrins with high reactivities and excellent enantioselectivities under basic reaction condition (up to > 99% conversion, 99% yield, > 99% ee). Moreover, gram-scale experiment was performed well in the presence of just 0.005 mol% (S/C = 20 000) Ir/f-amphox catalyst with 99% yield and > 99% ee.

The asymmetric hydrogenation of β-amino nitroolefins has been successfully achieved by rhodium/bis(phosphine)-thiourea L1 with excellent enantioselectivities and yields (up to 96% ee, 96% yield, >99% conversion, TON up to 1000) under mild conditions. Chiral β-amino nitroalkane products and their derivatives are versatile intermediates in organic synthesis.