结合光催化和ni -类氮核转移的区域选择性β-C(sp3)-H -酮的氨基化反应。

IF 5 1区化学 Q1 CHEMISTRY, ORGANIC

Organic Letters Pub Date : 2025-09-22 DOI:10.1021/acs.orglett.5c03178

Hyeyun Keum, , , Harin Ryoo, , , Dongwook Kim, , and , Sukbok Chang*,

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引用次数: 0

摘要

β-氨基羰基是生物活性分子和药物中普遍存在的具有合成价值的支架，但高效和选择性的合成方法尚不发达。本文公开了一种双光氧化还原/镍催化的平台，用于酮的β-C(sp3)-H酰胺化以获得β-氨基酮。该方法采用硅烯醇醚和二恶唑酮作为偶联剂，在温和的条件下实现了环酮和线性酮的区域选择性β-酰胺化。机理研究支持光生成的烯丙基碳自由基的参与，它与ni -类氮物质结合，促进C(sp3)-N键的形成。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Regioselective Formal β-C(sp3)–H Amidation of Ketones by Merging Photocatalysis and Ni-Nitrenoid Transfer

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Regioselective Formal β-C(sp3)–H Amidation of Ketones by Merging Photocatalysis and Ni-Nitrenoid Transfer

β-Amino carbonyls are synthetically valuable scaffolds that are prevalent in bioactive molecules and pharmaceuticals, yet efficient and selective methods for their synthesis remain underdeveloped. Disclosed herein is a dual photoredox/nickel-catalyzed platform for the formal β-C(sp³)–H amidation of ketones to access β-amido ketones. The method enables the regioselective β-amidation of both cyclic and linear ketones under mild conditions, employing silyl enol ethers and dioxazolones as readily available coupling partners. Mechanistic studies support the involvement of a photogenerated allylic carbon radical, which engages with Ni-nitrenoid species to facilitate C(sp³)–N bond formation.

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来源期刊

Organic Letters 化学-有机化学

CiteScore

9.30

自引率

11.50%

发文量

1607

审稿时长

1.5 months

期刊介绍： Organic Letters invites original reports of fundamental research in all branches of the theory and practice of organic, physical organic, organometallic,medicinal, and bioorganic chemistry. Organic Letters provides rapid disclosure of the key elements of significant studies that are of interest to a large portion of the organic community. In selecting manuscripts for publication, the Editors place emphasis on the originality, quality and wide interest of the work. Authors should provide enough background information to place the new disclosure in context and to justify the rapid publication format. Back-to-back Letters will be considered. Full details should be reserved for an Article, which should appear in due course.