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

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Title: Iridium-Catalyzed Enantioselective Transfer Hydrogenation of Ketones Controlled by Alcohol Hydrogen-Bonding and sp(3)-C-H Noncovalent Interactions
Authors: Murayama, Hiroaki Browse this author
Heike, Yoshito Browse this author
Higashida, Kosuke Browse this author
Shimizu, Yohei Browse this author
Yodsin, Nuttapon Browse this author
Wongnongwa, Yutthana Browse this author
Jungsuttiwong, Siriporn Browse this author
Mori, Seiji Browse this author
Sawamura, Masaya Browse this author →KAKEN DB
Keywords: transfer hydrogenation
chiral catalyst
C-H/pi interaction
nonclassical hydrogen bond
Issue Date: 4-Nov-2020
Publisher: Wiley-Blackwell
Journal Title: Advanced synthesis & catalysis
Volume: 362
Issue: 21
Start Page: 4655
End Page: 4661
Publisher DOI: 10.1002/adsc.202000615
Abstract: 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.
Rights: This is the peer reviewed version of the following article:Advanced synthesis & catalysis July 2020, which has been published in final form at This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.
Type: article (author version)
Appears in Collections:理学院・理学研究院 (Graduate School of Science / Faculty of Science) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)

Submitter: 澤村 正也

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