Journal
ADVANCED SYNTHESIS & CATALYSIS
Volume 362, Issue 21, Pages 4655-4661Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/adsc.202000615
Keywords
transfer hydrogenation; iridium; chiral catalyst; C-H/pi interaction; nonclassical hydrogen bond
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Funding
- MEXT KAKENHI [JP15H05801, JP18H04233]
- JSPS KAKENHI [JP18H03906]
- Sakura Science Plan through Collaborative research activity course from JST [S2018F0228129]
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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.
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