Asymmetric Cross-Dehydrogenative Coupling of Glycinates via Iodine-Mediated Photoredox/Lewis Acid Synergistic Catalysis

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL

ACS Catalysis Pub Date : 2025-05-22 DOI:10.1021/acscatal.5c02808

Jiuqi Tan, Hanyu Su, Min Chen, Fengnan Xiao, Longqing Yang, Xiaoming Feng, Liang-Wen Feng, Xiaohua Liu

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Abstract

The oxidative cross-dehydrogenative coupling (CDC) via α-carbonyl radicals significantly broadens the application scope of carbonyl compounds as synthons, offering a promising approach for carbon–carbon bond formation in organic synthesis. However, achieving cross-coupling and stereocontrol under mild reaction conditions has remained a significant challenge. Here, we report a synergistic catalytic platform that enables highly diastereo- and enantioselective CDC of β-keto carbonyls with glycine derivatives. The strategy introduces a photoredox catalyst and a chiral magnesium complex catalyst, leveraging the oxidations of the two coupling partners via independent pathways through the use of peroxybenzoate and a catalytic amount of NaI under visible-light irradiation. The β-carbonyl-substituted glycine derivatives can be readily obtained with exceptional stereocontrol (up to >19:1 dr, >99% ee) and yield, spanning a series of glycinates with both electron-donating and electron-withdrawing N-aryl substitutions. Mechanistic studies reveal a radical pathway rather than oxidative polar addition, showcasing a paradigm for merging photoredox-generated open-shell intermediates in C(sp³)–H cross-coupling.

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碘介导光氧化还原/Lewis酸协同催化下甘氨酸的不对称交叉脱氢偶联

α-羰基自由基氧化交叉脱氢偶联（CDC）极大地拓宽了羰基化合物作为合成子的应用范围，为有机合成中碳-碳键的形成提供了一种很有前景的途径。然而，在温和的反应条件下实现交叉耦合和立体控制仍然是一个重大挑战。在这里，我们报道了一个协同催化平台，使β-酮羰基与甘氨酸衍生物的高度非映对和对映选择性的CDC。该策略引入了一种光氧化还原催化剂和一种手性镁络合物催化剂，通过在可见光照射下使用过氧苯甲酸盐和NaI的催化量，利用两个偶联伙伴通过独立的途径进行氧化。β-羰基取代的甘氨酸衍生物具有优异的立体控制（高达19:1 dr， 99% ee）和产率，跨越了一系列具有供电子和吸电子n-芳基取代的甘氨酸。机制研究揭示了自由基途径而不是氧化极性加成，展示了在C(sp3) -H交叉偶联中合并光氧化还原生成的开壳中间体的范例。

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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.