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 sp³‐C−H/π interaction between an sp³‐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/sp³‐C−H⋅⋅⋅O two‐point hydrogen‐bonding between the chiral ligand and carbonyl group.

中文翻译：

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酒精氢键和sp3-CH非共价相互作用控制的铱催化的酮的对映选择性加氢

使用脯氨醇-膦手性配体开发了铱与甲酸的铱催化对映选择性转移氢化反应。铱原子与配体通过醇-醇盐相互转化的协同作用对于促进转移氢化至关重要。包括烷基芳基酮，酮酸酯和芳基杂芳基酮在内的各种酮是有效的底物。此催化的一个有吸引力的特征是酮的烷基和芳基取代基，促进与enantioselection的相同的有义氢化不管烷基取代基的空间位阻的需求，并因此导致高度对映选择性转移氢化的一种罕见的情况下之间的高效歧视叔-烷基芳基酮。量子化学计算表明SP ³ -C-H / AN之间π相互作用SP ³的脯氨醇-膦配位体的-C-H键和酮的芳基取代基是用于与O型H⋅⋅⋅O组合enantioselection关键/ SP ³ -手性配体与羰基之间存在CHH·⋅⋅O两点氢键。