Iridium‐Catalyzed Enantioselective Transfer Hydrogenation of Ketones Controlled by Alcohol Hydrogen‐Bonding and <i>sp</i><sup>3</sup>‐C−H Noncovalent Interactions
書誌事項
- タイトル別名
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- Iridium-Catalyzed Enantioselective Transfer Hydrogenation of Ketones Controlled by Alcohol Hydrogen-Bonding and sp(3)-C-H Noncovalent Interactions
説明
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.
収録刊行物
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- Advanced synthesis & catalysis
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Advanced synthesis & catalysis 362 (21), 4655-4661, 2020-11-04
Wiley-Blackwell
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詳細情報 詳細情報について
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- CRID
- 1050571470226717056
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- NII論文ID
- 120007168181
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- ISSN
- 16154169
- 16154150
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- HANDLE
- 2115/83157
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- 本文言語コード
- en
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- 資料種別
- journal article
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- データソース種別
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