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

doi:10.6023/cjoc202604039

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钯催化芳基溴化物与CO₂的羰化硫代酯基化反应

龙鑫^a,†, 孙丽伟^a,†, 李玉东^c, 王欢^b,*, 李跃辉^a,*

^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

收稿日期:2026-04-24 修回日期:2026-07-08
作者简介:^†共同第一作者
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.

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

Xin Long^a,†, Liwei Sun^a,†, Yudong Li^c, Huan Wang^b,*, Yuehui Li^a,*

^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

Received:2026-04-24 Revised:2026-07-08
Contact: ^*E-mail: liyuehui@sjtu.edu.cn; wanghuan00@qibebt.ac.cn
About author:^†These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China (No. 22572120) and National Key R&D Program of China (No. 2023YFA1507500).

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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

Cite this article

Xin Long, Liwei Sun, Yudong Li, Huan Wang, Yuehui Li. Palladium-Catalyzed Thiocarbonylation of Aryl Bromides to Produce Thioesters Using CO₂[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202604039.

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钯催化芳基溴化物与CO₂的羰化硫代酯基化反应

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

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钯催化芳基溴化物与CO2的羰化硫代酯基化反应