惰性键与二氧化碳的电化学羧化反应研究

doi:10.6023/cjoc202406045

摘要/Abstract

二氧化碳(CO₂)是一种绿色可再生的C1合成子, 通过与惰性键的羧化反应, 能够实现从简单分子到高附加值羧酸衍生物的直接转化, 兼具步骤经济性与原子经济性. 有机电合成是利用电子作“试剂”的绿色合成技术, 发展电化学促进的惰性键与二氧化碳的羧化反应成为近年研究热点. 按照C—H、C—C、C—O、C—F键的分类, 综述了二氧化碳参与惰性键的电还原羧化反应的研究成果, 着重讨论了反应机理及应用, 并对该领域发展趋势进行了展望.

关键词: 二氧化碳, 惰性键, 电化学, 还原羧化, 羧酸

Carbon dioxide (CO₂) is a green and renewable C1 synthon, and the direct carboxylation of inert chemical bonds with CO₂ could afford high value-added carboxylic acid derivatives from simple molecules, which feature both atomic and step economies. Organic electrosynthesis is a green synthesis technology using electrons as "reagents", and the development of electrochemical carboxylation of inert bonds with CO₂ has become a hot research topic in recent years. The recent progress on the electroreductive carboxylation of inert bonds with CO₂ is summarized, including C—H, C—C, C—O, and C—F single bonds. The mechanism and application of these reactions are emphatically discussed, and the challenges and development trends in this field are also covered.

Key words: carbon dioxide, inert chemical bonds, electrochemistry, reductive carboxylation, carboxylic acids

引用此文

高小童, 钟昱卿, 冯楠, 孙莹, 杨得勇, 周锋. 惰性键与二氧化碳的电化学羧化反应研究[J]. 有机化学, 2024, 44(10): 3043-3062.

Xiaotong Gao, Yuqing Zhong, Nan Feng, Ying Sun, Deyong Yang, Feng Zhou. Recent Advances in Electrochemical Carboxylation of Inert Chemical Bonds with Carbon Dioxide[J]. Chinese Journal of Organic Chemistry, 2024, 44(10): 3043-3062.

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图/表 23

图1. 代表性C—H、C—C、C—O及C—F惰性键的键解离能

Figure 1. BDEs of representative C—H, C—C, C—O and C—F inert bonds

图2. 惰性键与二氧化碳的电还原羧化反应

Figure 2. Electroreductive carboxylation of inert bonds with CO2

图式1. 氮杂芳烃C—H键的选择性电化学羧化反应

Scheme 1. Site-selective electrochemical carboxylation of C—H bonds in N-heteroarenes

图式2. 芳烃C—H键的位点选择性电化学羧化反应

Scheme 2. Site-selective electrochemical carboxylation of C—H bonds in arenes

图式3. 芳香醇苄位C—H键电催化羧化反应

Scheme 3. Electrocatalytic carboxylation of benzylic C—H bonds in aromatic alcohols

图式4. 张力环C—C单键电化学开环双羧基化反应

Scheme 4. Electrochemical ring-opening dicarboxylation of C—C single bonds in strained rings

图式5. 偕二氟环丙烷C—C单键电化学开环羧基化反应

Scheme 5. Electrochemical ring-opening carboxylation of C—C bonds in gem-difluorocyclopropanes

图式6. 环酮肟酯C—C单键电化学开环羧基化反应

Scheme 6. Electrochemical ring-opening carboxylation of C—C bonds in cycloketone oxime esters

图式7. 烯丙基酯C—O单键电化学区域选择性羧化反应

Scheme 7. Electrochemical regioselective carboxylation of C—O single bonds in allyl esters

图式8. 烯丙基酯C—O单键电化学羧化反应

Scheme 8. Electrocarboxylation of C—O single bonds in allyl esters

图式9. 炔丙基乙酸酯C—O单键电化学羧化反应

Scheme 9. Electrocarboxylation of C—O single bonds in propargylic acetates

图式10. 炔丙基碳酸酯C—O单键不对称电催化羧化反应

Scheme 10. Asymmetric electrocatalytic carboxylation of C—O single bonds in propargylic carbonates

图式11. 苯甲醛二乙缩醛C—O单键电化学羧化反应

Scheme 11. Electrocarboxylation of C—O single bonds in benzal diacetates

图式12. 磷酸苄酯和亚磷酸苄酯C—O单键电化学羧化反应

Scheme 12. Electrocarboxylation of C—O single bonds in benzylic phosphates and phosphinates

图式13. 芳基甲醇C—O单键电化学羧化反应

Scheme 13. Electrocarboxylation of C—O single bonds in aryl methanols

图式14. 基于微流控电化学的联苯甲醇C—O单键的羧化反应

Scheme 14. Micro-electro-flow induced carboxylation of C—O single bonds in biphenylmethanol

图式15. 环氧化合物C—O键的开环电羧化反应

Scheme 15. Electrocarboxylation of C—O single bonds in epoxides

图式16. 芳基环氧C—O单键电化学羧化反应

Scheme 16. Electrochemical carboxylation of C—O single bonds in aryl epoxides

图式17. 1,3-噁唑烷-2-酮C(sp3)—O键的电化学羧化反应

Scheme 17. Electrocarboxylation of C(sp3)—O single bonds in 1,3-oxazolidin-2-ones

图式18. 环状碳酸酯C—O键的电化学羧化反应

Scheme 18. Electrocarboxylation of C—O single bonds in cyclic carbonate

图式19. α-三氟甲基烯烃C—F键的电化学脱氟羧化反应

Scheme 19. Electrochemical defluorinative carboxylation of C—F bonds in α-CF3 alkenes

图式20. 偕二氟烯烃C—F键的电化学脱氟羧化反应

Scheme 20. Electrochemical defluorinative carboxylation of C—F bonds in gem-difluoroalkenes

图式21. 三氟甲基(杂)芳烃C—F键的电化学脱氟羧化反应

Scheme 21. Electrochemical defluorinative carboxylation of C—F bonds in trifluoromethyl (hetero)arenes

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