电化学催化下的多氟烷基化反应研究进展

doi:10.6023/cjoc202008017

摘要/Abstract

氟化学已经在各行各业受到广泛应用, 氟化学和有机化学的结合也遍地生花. 由于将氟原子或氟基团引入到药物中具有重要意义, 因此寻求一种有效的氟烷基化途径至关重要. 随着电化学的发展, 人们将电化学和氟烷基化反应进行了巧妙地结合. 进而得到了更加安全、经济、环保并且高效的氟烷基化途径. 在电化学指导下的氟烷基化反应途径, 不仅在反应方式方面进行了革新, 同样在底物普适性方面也具有优势. 针对不饱和脂肪族化合物及其衍生物和芳香族化合物的电化学催化下的氟烷基化反应已经有诸多报道. 根据底物的性质及其反应机理总结了电催化下氟烷基化方法的进展.

关键词: 电化学, 氟化学, 氟烷基化反应, 烯烃, 芳烃

Fluorine chemistry has been widely used in all walks of life, and the combination of fluorine chemistry and organic chemistry is blooming everywhere. Since the introduction of fluorine atoms or fluorine groups into drugs is of great significance, it is essential to seek an effective fluoroalkylation pathway. With the development of electrochemistry, people combine electrochemistry and fluoroalkylation reaction skillfully. In turn, a safer, more economical, environmentally friendly and efficient fluoroalkylation pathway is obtained. The fluoroalkylation reaction pathway under the guidance of electrochemistry has not only reformed the reaction method, but also has advantages in terms of substrate universality. Fluoroalkylation of unsaturated aliphatic compounds their derivatives and aromatic compounds under electrochemical catalysis has been reported. According to the nature of the substrate and its reaction mechanism, the progress of electrocatalytic fluoroalkylation methods is summarized.

Key words: electrochemistry, fluorochemistry, fluoroalkylation reaction, olefin, aromatic

引用此文

刘颖杰, 韩莹徽, 林立青, 许颖. 电化学催化下的多氟烷基化反应研究进展[J]. 有机化学, 2021, 41(3): 934-946.

Yingjie Liu, Yinghui Han, Liqing Lin, Ying Xu. Research Progress of Polyfluoroalkylation Reaction under Electrochemical Catalysis[J]. Chinese Journal of Organic Chemistry, 2021, 41(3): 934-946.

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图/表 22

图式1. 丙烯酸酯的二氟和三氟甲基化

Scheme 1. Difluoro and trifluoromethylation of acrylate

图式2. 4-叔丁基苯乙烯为模型底物的三氟甲基化反应

Scheme 2. Trifluoromethylation of 4-tert-butylstyrene as a model substrate

图式3. 烯烃的电催化氯三氟甲基化

Scheme 3. Electrocatalytic chlorotrifluoromethylation of alkenes

图式4. Lewis酸催化电化学氧化烯烃的三氟甲基化双官能化

Scheme 4. Electrochemical oxidation with Lewis-acid catalysis leading to trifluoromethylative difunctionalization of alkenes

图式5. 1,2-迁移的烯丙醇的电化学氧化芳基(烷基)三氟甲基化

Scheme 5. Electrochemical oxidative aryl(alkyl)trifluorome- thylation of allyl alcohols via 1,2-migration

图式6. 烯烃的电化学自由基甲酰氧基化-溴化、-氯化和-三氟甲基化

Scheme 6. Electrochemical radical formyloxylation-bromina- tion, -chlorination, and -trifluoromethylation of alkenes

图式7. 电化学促进的未活化烯烃的氟代烷基化-迁移反应

Scheme 7. Electrochemically promoted fluoroalkylation-distal functionalization of unactivated alkenes

图式8. 烯醇类化合物的电化学三氟甲基化

Scheme 8. Electrochemical trifluoromethylation of enol compounds

图式9. N-氰胺-烯烃的自由基环合反应

Scheme 9. Radical cyclization reaction of N-cyanamide-olefin

图式10. 烯丙醇的电化学三氟甲基化

Scheme 10. Electrochemical trifluoromethylation of allyl alcohol

图式11. Langlois作为碳源的三氟甲基化反应

Scheme 11. Trifluoromethylation reaction with Langlois as a carbon source

图式12. 炔烃的电化学二氟甲基芳基化

Scheme 12. Electrochemical difluoromethylarylation of alkynes

图式13. 电化学氟甲基化在半水条件下引发烯烃的内酯化

Scheme 13. Electrochemical fluoromethylation triggered lactonizations of alkenes under semi-aqueous conditions

图式14. CF3SO2Na对α,β-不饱和羧酸的电化学脱羧三氟甲基化作用

Scheme 14. Electrochemical decarboxylative trifluoromethylation of α,β-unsaturated carboxylic acids with CF 3SO2Na

图式15. 电催化芳族化合物的氟烷基化反应

Scheme 15. Electrocatalytic fluoroalkylation of aromatic compounds

图式16. 芳香族化合物的自由基三氟甲基化和全氟烷基化

Scheme 16. Free radical trifluoromethylation and perfluoroalkylation of aromatic compounds

图式17. 非官能化芳香族化合物的氟烷基化反应

Scheme 17. Fluoroalkylation reaction of non-functionalized aromatic compounds

图式18. 三氟甲基三乙铵络合物实现的芳烃和杂芳烃的阴极C—H三氟甲基化

Scheme 18. Cathodic C—H trifluoromethylation of arenes and heteroarenes enabled by an in triflyltriethylammonium complex

图式19. ACE对(杂)芳烃进行三氟甲基化

Scheme 19. Trifluoromethylation of (hetero)arenes by ACE

图式20. 咪唑类化合物的C—H功能化反应

Scheme 20. C—H functionalization reaction of imidazole compounds

图式21. 异烟酸酰肼的三氟甲基化反应

Scheme 21. Trifluoromethylation reaction of isonicotinic acid hydrazide

图式22. 溴离子介导的缺电子杂环的三氟甲基化反应

Scheme 22. Bromide ion-mediated trifluoromethylation of electron-deficient heterocycles

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