Rhodium-Catalyzed Homogeneous Asymmetric Hydrogenation of Naphthol Derivatives

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 29, 2025

Due to their strong aromaticity and difficulties in chemo-, regio-, enantioselectivity control, asymmetric hydrogenation of naphthol derivatives 1,2,3,4-tetrahydronaphthols has remained a long-standing challenge. Herein, we report the first example homogeneous catalyzed by tethered rhodium-diamine catalysts, affording wide array optically pure high yields with excellent enantioselectivities (up 98% yield >99% ee). Mechanistic studies experimental computational approaches reveal that fluorinated solvent 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) plays vital roles control reactivity selectivity, 1-naphthol is reduced via cascade reaction pathway, including dearomative tautomerization, 1,4-hydride addition, 1,2-hydride addition sequence. A novel synergistic activation mode was proposed which HFIP assists both hydrogen molecule presence base, situ-generated fleeting keto tautomer immediately trapped Rh(III)-H species before it escapes from cage. This protocol provides straightforward practical pathway for synthesis key intermediates several chiral drugs. Particularly, Nadolol, drug treatment hypertension, angina pectoris, congestive heart failure, certain arrhythmias, enantioselectively synthesized time.

Language: Английский

Ruthenium-Catalyzed Asymmetric trans-Selective Hydrogenation of 2,3-Disubstituted Quinoxaline Derivatives

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

The asymmetric trans-selective hydrogenation of arenes has long been a significant challenge. In this work, we were able to control the trans/cis selectivity in ruthenium-catalyzed 2,3-disubstituted quinoxalines by varying catalyst counteranion. Using density functional theory calculations, investigated weak interactions─such as CH/π and hydrogen bonding─among counteranion, framework, substrate, elucidating fundamental influence counteranions on quinoxalines.

Language: Английский

Transition Metal Catalyzed Carbocycle-Selective Asymmetric Hydrogenation of Aromatic Rings

Chinese Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 44(7), P. 2063 - 2063

Published: Jan. 1, 2024

Language: Английский