光催化钴催化脱氢对杂环内酰胺的动力学拆分。

IF 15.6 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of the American Chemical Society Pub Date : 2025-07-10 DOI:10.1021/jacs.5c07524

Chao Zhou,Thorsten Bach

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引用次数: 0

摘要

手性杂环内酰胺类化合物通过手性二苯甲酮催化剂选择性抽氢的光化学过程进行了动力学分解。对一个对映体的识别是通过两点氢键相互作用实现的，该相互作用将光催化剂的活性羰基指向内酰胺中立体中心的C-H键。生成的自由基在钴胺肟催化脱氢反应中转化为氧化产物。未反应性对映体被保留并分离为对映体富集形式（21例，产率31-56%，ee 90-99%）。

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Kinetic Resolution of Heterocyclic Lactams by a Photocatalytic Cobalt-Catalyzed Dehydrogenation.

Chiral heterocyclic lactams have been kinetically resolved in a photochemical process that involves selective hydrogen abstraction by a chiral benzophenone catalyst. Recognition of one enantiomer is achieved by a two-point hydrogen bonding interaction that directs the reactive carbonyl group of the photocatalyst to the C-H bond at the stereogenic center within the lactam. The generated radical is converted to an oxidized product in a cobaloxime-catalyzed dehydrogenation reaction. The unreactive enantiomer is retained and isolated in enantiomerically enriched form (21 examples, 31-56% yield, 90-99% ee).

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来源期刊

Journal of the American Chemical Society 化学-化学综合

CiteScore

24.40

自引率

6.00%

发文量

2398

审稿时长

1.6 months

期刊介绍： The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.