Highly Enantioselective Iridium-Catalyzed Hydrogenation of o-Amidophenyl Ketones Enabled by 1,2-Diphenylethylenediamine- Derived P,N,N-Ligands with Tertiary Amine Terminus

A readily available and highly modular class of chiral P,N,N-ligands based on a structurally flexible nonchiral phosphineamine framework with an optically active 1,2-diphenylethylenediamine unit bearing a tertiary amine terminus as the chiral source have been developed and successfully applied in the Ir-catalyzed asymmetric hydrogenation of o-amidophenyl ketones. These tridentate P,N,N-ligands exhibited excellent activity, enantioselectivity, and substrate tolerance, thus furnishing various optically active o-amidobenzhydrols in up to 99% yields and with >99% ee. The utility of this protocol has been proven by synthetically diverse product transformation and highly enantioselective production of a rice plant growth regulator, (S)-inabenfide.

Automated summary

A readily available and highly modular class of chiral P,N,N-ligands have been developed and successfully applied in the Ir-catalyzed asymmetric hydrogenation. These ligands exhibited excellent activity, enantioselectivity, and substrate tolerance, thus providing optically active compounds with high yields and enantioselectivities. This study demonstrates the utility of these ligands in diverse product transformation and the synthesis of biologically active compounds.