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Iridium-Catalyzed Enantioselective Transfer Hydrogenation of Ketones Controlled by Alcohol Hydrogen-Bonding and sp(3)-C-H Noncovalent Interactions
| 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 | | iridium | | 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 https://onlinelibrary.wiley.com/doi/full/10.1002/adsc.202000615. 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) |
| URI: | http://hdl.handle.net/2115/83157 |
| 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)
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Submitter: 澤村 正也
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