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新疆大学张永红/刘晨江ACIE:电化学调控实现以二氧化碳为羧基源实现炔烃的发散性羧基化和氢羧基化反应

发布时间:2025-11-21      浏览量:

图1. TOC (图片来源于ACIE)
摘要:
Carboxylation and hydrocarboxylation of alkynes with CO2 for the synthesis of value-added and versatile carboxylic acids are of great importance. However, harsh reaction conditions, poor selectivity, practicability, and sustainability have always restricted its application. Electrochemical synthesis has been considered as a practical and environmentally friendly organic synthesis strategy via a tunable redox process. Hence, herein, an efficient electrochemical controllable divergent carboxylation and hydrocarboxylation of alkynes with CO2 was achieved to overcome the limitation of traditional methods. Four kinds of arylpropiolic acid, cinnamic acid, fumaric acid, succinic acid, and their derivatives can be obtained with good selectivity by regulating substrates, solvents, and electrolytes. The method features broad substrate scope, divergent transformation with good selectivity, scalability, additional reducing agent-, hydrogen donor-, metal-, and ligand-free conditions, which offer novel insights into electrochemically driven CO2 fixation and alkyne functionalization.
研究背景:

19D70

图2. 研究背景及本策略 (图片来源于ACIE)
研究内容:

20B0B

图3. 条件优化 (图片来源于ACIE)

10AE0


图4. 炔烃的单羧基化和双羧基化反应底物拓展 (图片来源于ACIE)

20EE1

图5. 炔烃的氢羧基化和两次氢羧基化反应底物拓展 (图片来源于ACIE)

1AD41

图6. 机理研究 (图片来源于ACIE)

1035D

图7. 可能的反应机理 (图片来源于ACIE)
总结:
In summary, we developed an electrochemical controllable divergent carboxylation and hydrocarboxylation of alkynes with CO2 under mild conditions. The arylpropiolic acid, cinnamic acid, fumaric acid, and succinic acid derivatives were efficiently afforded with good yield and selectivity under the present electrochemical conditions. The methods feature broad substrate scope, divergent transformation with good selectivity, scalability, under additional reducing agent , hydrogen donor-, metal-, ligand-free, and mild conditions. The developed electrochemical carbon capture and divergent conversion strategy provides a new pathway for the high value utilization of CO2 and enables the efficient preparation of acid intermediates for the synthesis of various natural products and pharmaceutical molecules.
文献信息:
Haomin Chen+, Xiuli Zhao+, Bin Wang, Ziren Chen, Fei Xue, Yu Xia, Shaofeng Wu, Chenjiang Liu,* and Yonghong Zhang*, Electrochemical Controllable Divergent Carboxylation and Hydrocarboxylation of Alkynes with CO2, Angew. Chem. Int. Ed., 2025, e20335.