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DOI: https://doi.org/10.6023/cjoc202604039

研究论文

钯催化芳基溴化物与CO2的羰化硫代酯基化反应

  • 龙鑫 ,
  • 孙丽伟 ,
  • 李玉东 ,
  • 王欢 ,
  • 李跃辉
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  • a智慧能源创新学院 上海交通大学 上海 200240;
    b太阳能光电转化与利用重点实验室 青岛生物能源与过程研究所 中国科学院 青岛 266101;
    c新疆极端环境电子学重点实验室 特殊环境功能材料与器件重点实验室 新疆理化技术研究所 中国科学院 乌鲁木齐 830011
†共同第一作者

收稿日期: 2026-04-24

  修回日期: 2026-07-08

  网络出版日期: 2026-08-24

基金资助

国家自然科学基金(No. 22572120)和国家重点研发计划(No. 2023YFA1507500)资助项目.

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Palladium-Catalyzed Thiocarbonylation of Aryl Bromides to Produce Thioesters Using CO2

  • Xin Long ,
  • Liwei Sun ,
  • Yudong Li ,
  • Huan Wang ,
  • Yuehui Li
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  • aCollege of Smart Energy, Shanghai Jiao Tong University, Shanghai, 200240;
    bKey Laboratory of Photoelectric Conversion and Utilization of Solar Energy, Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, 266101;
    cXinjiang Key Laboratory of Extreme Environment Electronics, Key Laboratory of Functional Materials and Devices for Special Environmental Conditions, Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Urumqi, 830011
†These authors contributed equally to this work.

Received date: 2026-04-24

  Revised date: 2026-07-08

  Online published: 2026-08-24

Supported by

National Natural Science Foundation of China (No. 22572120) and National Key R&D Program of China (No. 2023YFA1507500).

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摘要

以CO2作为羰基源,实现了钯催化的芳基溴化物的高效羰化硫代酯基化反应。该体系的关键在于使用新型咔唑衍生膦配体与Pd盐配位形成的催化剂,使反应在低催化剂载量（1 mol%）和相对温和反应条件（120 °C,5 bar CO2）下发生,一系列带有吸电子或给电子基团的芳基溴化物均可有效发生烷硫羰基化反应,最高收率达95%（21个实例）。机理研究表明,该反应经由苯硅烷将CO2原位还原为CO,随后发生钯催化的羰基化交叉偶联过程。该方法为拓展CO替代物进行羰基化反应提供了一种新的反应路线方案。

关键词： 钯催化; 烷硫羰基化; 芳基溴化物; 硫酯; 二氧化碳; 咔唑衍生膦配体

本文引用格式

龙鑫 , 孙丽伟 , 李玉东 , 王欢 , 李跃辉 . 钯催化芳基溴化物与CO2的羰化硫代酯基化反应[J]. 有机化学, 0 : 202604039 . DOI: 10.6023/cjoc202604039

Abstract

A general and efficient palladium-catalyzed thiocarbonylation of aryl bromides using CO2 as a renewable and non-toxic C1 resource has been established. The key to this transformation is a newly designed carbazole-derived phosphine ligand in combination with PdCl2, enabling low catalyst loading (1 mol%) and mild reaction conditions (120 °C, 5 bar CO2). The thiocarbonylation of a series of aryl bromides bearing electron-withdrawing or electron-donating groups can be effectively carried out, affording up to 95% yield (21 examples). Mechanistic studies suggest that the reaction proceeds via in situ reduction of CO2 to CO by phenylsilane, followed by palladium-catalyzed carbonylative cross-coupling. This method offers a safer and more sustainable alternative to traditional approaches that rely on toxic CO gas.

Key words： palladium catalysis; thiocarbonylation; aryl bromides; thioesters; carbon dioxide; carbazole-derived phosphine ligand

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