Iridium-Catalyzed Enantioselective Transfer Hydrogenation of Ketones Controlled by Alcohol Hydrogen-Bonding and sp(3)-C-H Noncovalent Interactions

DOI IR (HANDLE) HANDLE Web Site Web Site View 1 Remaining Hide Research Data 2 Citations 52 References Open Access

Bibliographic Information

Other Title
  • Iridium‐Catalyzed Enantioselective Transfer Hydrogenation of Ketones Controlled by Alcohol Hydrogen‐Bonding and <i>sp</i><sup>3</sup>‐C−H Noncovalent Interactions

Description

Iridium-catalyzed enantioselective transfer hydrogenation of ketones with formic acid was developed using a prolinol-phosphine chiral ligand. Cooperative action of the iridium atom and the ligand through alcohol-alkoxide interconversion is crucial to facilitate the transfer hydrogenation. Various ketones including alkyl aryl ketones, ketoesters, and an aryl heteroaryl ketone were competent substrates. An attractive feature of this catalysis is efficient discrimination between the alkyl and aryl substituents of the ketones, promoting hydrogenation with the identical sense of enantioselection regardless of steric demand of the alkyl substituent and thus resulting in a rare case of highly enantioselective transfer hydrogenation of tert-alkyl aryl ketones. Quantum chemical calculations revealed that the sp(3)-C-H/pi interaction between an sp(3)-C-H bond of the prolinol-phosphine ligand and the aryl substituent of the ketone is crucial for the enantioselection in combination with O-H center dot center dot center dot O/sp(3)-C-H center dot center dot center dot O two-point hydrogen-bonding between the chiral ligand and carbonyl group.

Journal

Citations (2)*help

See more

References(52)*help

See more

Related Data

See more

Related Projects

See more

Keywords

Details 詳細情報について

Report a problem

Back to top