Photoredox/HAT-Catalyzed Dearomative Nucleophilic Addition of the CO2 Radical Anion to (Hetero)Aromatics
Photoredox/HAT-Catalyzed Dearomative Nucleophilic Addition of the CO2 Radical Anion to (Hetero)Aromatics
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DOI：
10.1021/acscatal.2c06192
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发表时间：
2023-02
期刊：
影响因子：
12.9
通讯作者：
S. Mangaonkar;Hiroki Hayashi;Hideaki Takano;Wataru Kanna;Satoshi Maeda;Tsuyoshi Mita
中科院分区：
文献类型：
--
作者：
S. Mangaonkar;Hiroki Hayashi;Hideaki Takano;Wataru Kanna;Satoshi Maeda;Tsuyoshi Mita
CO2自由基阴离子（CO2·-）是一种强亲核自由基，在现代有机化学中有着广泛的应用。这种自由基物种在单电子还原反应中表现出高反应性，这是由于同时释放稳定的CO2或Giese型反应，特别是对于缺电子烯烃和苯乙烯衍生物。与先前的报道相比，我们在本文中公开了用于将CO2·-（其可以在光氧化还原/氢原子转移（HAT）催化下由甲酸铯产生）引入稳定的杂芳族化合物如苯并呋喃、苯并噻吩和吲哚衍生物中以中等至高产率提供合成有用的α-氧基、α-硫代和α-氨基酸衍生物的稳健方法的开发。此外，当使用缺电子萘衍生物时，单电子还原和Giese型亲核加成同时发生，以良好的产率产生羧基化四氢萘衍生物。此外，带有氰基的四氢萘之一通过氢化还原氰基官能团，然后环化转化为相应的γ-丁内酰胺。据我们所知，在光氧化还原/HAT条件下与金属甲酸盐的这些脱芳羧化反应是前所未有的，因此提供了将C1源引入稳定（杂）芳族化合物的合成选择。
The radical anion of CO2(CO2•–) is a strongly nucleophilic radical species with rapidly emerging applications in contemporary organic chemistry. This radical species exhibits high reactivity in single-electron reduction reactions due to the concomitant release of stable CO2, or Giese-type reactions, especially for electron-deficient alkenes and styrene derivatives. In contrast to previous reports, we herein disclose the development of a robust method for the introduction of CO2•–, which can be generated from cesium formate under photoredox/hydrogen atom transfer (HAT) catalysis, into stable heteroaromatics such as benzofuran, benzothiophene, and indole derivatives to afford synthetically useful α-oxy, α-thio, and α-amino acid derivatives in moderate to high yield. In addition, when using electron-deficient naphthalene derivatives, both single-electron reduction and Giese-type nucleophilic addition occur simultaneously to produce carboxylated tetrahydronaphthalene derivatives in good yield. Moreover, one of the tetrahydronaphthalenes that bear a cyano group was transformed into the corresponding γ-butyrolactam via reduction of the cyano functionality through hydrogenation followed by cyclization. To the best of our knowledge, these dearomative carboxylation reactions with metal formates under photoredox/HAT conditions are unprecedented, thus providing a synthetic option for the introduction of a C1 source into stable (hetero)aromatics.