Tang Shibiao, Tao Senze, Yang Ke, Li Bin, Wang Baiquan
State Key Laboratory of Elemento-Organic Chemistry, Frontiers Science Center for New Organic Matter, College of Chemistry, Nankai University, Tianjin 300071, China.
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, China.
Org Lett. 2025 Jul 4;27(26):7194-7199. doi: 10.1021/acs.orglett.5c02130. Epub 2025 Jun 24.
C-C bond formation catalyzed by abundant and nontoxic iron has attracted increasing attention. Although much progress has been made, iron-catalyzed reductive coupling is still limited. In this work, the reductive carboxylation of aryl thianthrenium salts with CO catalyzed by iron is developed. This protocol is characterized by mild conditions and excellent functional group tolerance. Due to the nontoxicity of iron, this method can be applied for the late-stage C-H carboxylation of complex drug molecules to provide multiple carboxyl drugs. Preliminary mechanistic studies reveal that an Fe(0)-Fe(I)-Fe(II)-Fe(0) catalytic cycle may be involved in this reaction. This reaction expands the types of iron-catalyzed reactions, which may promote the application of iron catalysis in organic synthesis.
由丰富且无毒的铁催化的碳-碳键形成受到了越来越多的关注。尽管已取得了很大进展，但铁催化的还原偶联反应仍然有限。在这项工作中，开发了铁催化芳基噻蒽鎓盐与一氧化碳的还原羧基化反应。该方法具有条件温和、官能团耐受性优异的特点。由于铁的无毒特性，此方法可应用于复杂药物分子的后期碳-氢羧基化反应，以提供多种含羧基的药物。初步机理研究表明，该反应可能涉及一个铁(0)-铁(I)-铁(II)-铁(0)的催化循环。此反应扩展了铁催化反应的类型，这可能会促进铁催化在有机合成中的应用。
