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Iridium‐Catalyzed Enantioselective Transfer Hydrogenation of Ketones Controlled by Alcohol Hydrogen‐Bonding and sp 3 ‐C−H Noncovalent Interactions
Author(s) -
Murayama Hiroaki,
Heike Yoshito,
Higashida Kosuke,
Shimizu Yohei,
Yodsin Nuttapon,
Wonggwa Yutthana,
Jungsuttiwong Siriporn,
Mori Seiji,
Sawamura Masaya
Publication year - 2020
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.202000615
Subject(s) - chemistry , enantioselective synthesis , transfer hydrogenation , ketone , aryl , substituent , alkyl , medicinal chemistry , iridium , ligand (biochemistry) , noyori asymmetric hydrogenation , phosphine , steric effects , catalysis , stereochemistry , organic chemistry , ruthenium , biochemistry , receptor
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/π 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⋅⋅⋅O/ sp 3 ‐C−H⋅⋅⋅O two‐point hydrogen‐bonding between the chiral ligand and carbonyl group.