化学
氢原子
光化学
对偶(语法数字)
Atom(片上系统)
有机化学
艺术
烷基
文学类
计算机科学
嵌入式系统
作者
Xiaoyu Yan,Yubing Pang,Yutong Zhou,Rui Chang,Juntao Ye
摘要
Photochemical deracemization has emerged as one of the most straightforward approaches to access highly enantioenriched compounds in recent years. While excited-state events such as energy transfer, single electron transfer, and ligand-to-metal charge transfer have been leveraged to promote stereoablation, approaches relying on hydrogen atom transfer, which circumvent the limitations imposed by the triplet energy and redox potential of racemic substrates, remain underexplored. Conceptually, the most attractive method for tertiary stereocenter deracemization might be hydrogen atom abstraction followed by hydrogen atom donation. However, implementing such a strategy poses significant challenges, primarily because the enantioenriched products are also reactive if the chiral catalyst is unable to differentiate between the two enantiomers. Herein we report a distinct dual hydrogen atom transfer strategy for photochemical deracemization of δ- and γ-lactams, achieving high enantioenrichment and deuterium incorporation despite the inherent reactivity of the products. Mechanistic studies reveal that benzophenone enables nonselective hydrogen atom abstraction while a tetrapeptide-derived thiol dictates the enantioselectivity of the hydrogen atom donation step. More importantly, a pyridine-based alcohol was found to play crucial roles in facilitating the hydrogen atom abstraction as well as enhancing the enantioselectivity of the hydrogen atom donation step.
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