通过自由基介导的异构反应立体异构制备烯酰胺

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-04-10 DOI:10.1021/acscatal.5c00583

Yingying Xu, Xin Zhang, Xiao Kang, Kai Xu, Gangguo Zhu, Xi-Jia Liu

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引用次数: 0

摘要

以相同的起始材料进行立体发散合成在化学领域具有很高的吸引力，但也具有挑战性。本文描述了一种前所未有的自由基介导的芳基甲基肠腈和n -甲基酰胺之间的等血凝反应。这种集成的光化学策略使得(E)-和(Z)-酰胺在非常温和的条件下发散合成。特别是，它可以以95%的氘掺入率制备模块化的(E)-α-氘酰胺，这是对酰胺生产研究工具包的一个非常有价值的补充。天然产物阿拉他胺及其氘标记类似物的合成也证明了该方案的实用性。机理研究表明，在十钨酸钠（NaDT）催化剂的存在下，通过光诱导氢原子转移（HAT）产生的两个连续的烷基自由基世代是该等速反应所必需的，并且E/Z选择性由助催化剂调节。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Stereodivergent Construction of Enamides via a Radical-Mediated Isodesmic Reaction

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Stereodivergent Construction of Enamides via a Radical-Mediated Isodesmic Reaction

Stereodivergent synthesis from the same starting materials is highly attractive but challenging in chemistry. Here, an unprecedented radical-mediated isodesmic reaction between aryl methylenemalononitriles and N-methyl amides is described. This integrated photochemical strategy enables the divergent synthesis of both (E)- and (Z)-enamides under very mild conditions. Particularly, it can prepare modularly (E)-α-deuterium enamides with >95% deuterium incorporation, representing a highly valuable addition to the research toolkit for enamide production. The utility of this protocol is also demonstrated by the synthesis of natural product alatamide and its deuterium-labeled analog. Mechanistic studies reveal that two sequential alkyl radical generations via photoinduced hydrogen atom transfer (HAT) in the presence of a sodium decatungstate (NaDT) catalyst are essential for this isodesmic reaction, and E/Z selectivities are adjusted by cocatalysts.

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.