电化学促进未活化C(sp3)—H官能团化研究进展

doi:10.6023/cjoc202309024

摘要/Abstract

有机电合成以无痕电子代替传统的化学氧化剂或还原剂, 具有绿色易放大等优势. 未活化C(sp³)—H键的官能团化可以将目标官能团直接引入分子中进行修饰, 避免预官能团化, 兼具原子经济性和步骤经济性. 随着有机电合成发展的日益成熟, 电化学促进未活化C(sp³)—H官能团化成为了有机合成的研究热点之一. 根据官能团类型对反应进行分类, 总结了近年来涉及未活化C(sp³)—H官能化的研究成果, 重点分析了反应优势、底物特点以及反应机理, 最后展望了面临的挑战及未来的发展趋势.

关键词: 有机电合成, 未活化C(sp³)—H键, 官能团化

Organic electrosynthesis replaces traditional chemical oxidants or reductants with traceless electrons, which has the advantages of sustainability and easy to scale up. The functionalization of unactivated C(sp³)—H bond can directly introduce the target functional group into the molecules, avoiding pre-functionalization and possessing both atomic and step economies. With the development of organic electrosynthesis, electrochemical-promoted functionalization of unactivated C(sp³)—H bond has become one of the hotspots in organic synthesis. The functional groups are classified according to the types of functional groups, and the recent achievements related to the functionalization of unactivated C(sp³)—H bond are summarized, with emphasis on analyzing reaction advantages, substrate scope, and reaction mechanism. Finally, the current challenges and future development are briefly discussed.

Key words: organic electrosynthesis, unactivated C(sp³)—H bond, functionalization

引用此文

高瑞林, 文丽荣, 郭维斯. 电化学促进未活化C(sp³)—H官能团化研究进展[J]. 有机化学, 2024, 44(3): 892-902.

Ruilin Gao, Lirong Wen, Weisi Guo. Recent Advances in Electrochemical-Promoted Unactivated C(sp³)—H Functionalization[J]. Chinese Journal of Organic Chemistry, 2024, 44(3): 892-902.

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图/表 15

图1. C(sp3)—H键的BDE

Figure 1. BDE of C(sp3)—H bond

图式1. 反应模式

Scheme 1. Reaction activation mode

图式2. 奎宁环介导的电化学促进未活化C(sp3)—H键氧化

Scheme 2. Electrochemical-promoted oxidation of unactivated C(sp3)—H bond mediated by quinuclidine

图式3. N-铵基叶立德介导的电化学促进未活化C(sp3)—H键氧化

Scheme 3. Electrochemical-promoted oxidation of unactivated C(sp3)—H bond mediated by N-ammonium ylide

图式4. 电化学促进未活化C(sp3)—H键羟基化

Scheme 4. Electrochemical-promoted hydroxylation of unactivated C(sp3)—H bond

图式5. 电化学促进钯催化未活化C(sp3)—H键氧化

Scheme 5. Electrochemical-promoted oxidation of unactivated C(sp3)—H bond catalyzed by palladium

图式6. 光电协同催化未活化C(sp3)—H键氧化

Scheme 6. Photoelectrocatalyzed oxidation of unactivated C(sp3)—H bond

图式7. 光电协同催化未活化C(sp3)—H键叠氮化

Scheme 7. Photoelectrocatalyzed azidation of unactivated C(sp3)—H bond

图式8. 电化学促进锰催化未活化C(sp3)—H键叠氮化

Scheme 8. Electrochemical-promoted azidation of unactivated C(sp3)—H bond catalyzed by manganese

图式9. 电化学促进未活化C(sp3)—H键胺化

Scheme 9. Electrochemical-promoted amination of unactivated C(sp3)—H bond

图式10. 光电协同催化未活化C(sp3)—H键杂芳化

Scheme 10. Photoelectrocatalyzed for heteroaromatization of unactivated C(sp3)—H bond

图式11. 电化学促进未活化C(sp3)—H键杂芳化

Scheme 11. Electrochemical-promoted heteroaromatization of unactivated C(sp3)—H bond

图式12. 光电协同催化未活化C(sp3)—H与苯并噻唑的交叉偶联

Scheme 12. Photoelectrocatalyzed cross coupling of unactivated C(sp3)—H bond with benzothiazoles

图式13. 电化学促进未活化C(sp3)—H键氟化

Scheme 13. Electrochemical-promoted fluorination of unactivated C(sp3)—H bond

图式14. 电化学促进未活化C(sp3)—H键烯基化和酰基化

Scheme 14. Electrochemical-promoted alkenylation and acylation of unactivated C(sp3)—H bond

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电化学促进未活化C(sp³)—H官能团化研究进展

Recent Advances in Electrochemical-Promoted Unactivated C(sp³)—H Functionalization

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