水溶液中的Minisci反应研究进展

doi:10.6023/cjoc202401015

摘要/Abstract

Minisci反应是通过自由基中间体对缺电子含氮杂环化合物进行官能团化的方法. 利用Minisci反应可以向未官能团化的缺电子含氮杂环上引入烷基、酰基、硅基、烷硫基、硼烷等, 构建具有不同取代基的杂环化合物, 是合成取代杂环的一个重要手段. 水作为一种绿色环保的溶剂, 是进行有机反应的理想介质, 在Minisci反应中得到了广泛应用. 尽管从发现Minisci反应开始, 水作为Minisci反应的介质就得到应用, 但是水溶液中的Minisci反应仍然发展缓慢. 从烷基化、芳基化和酰基化三个方面, 根据不同的自由基前体, 综述了水溶液中Minisci反应的进展.

关键词: Minisci反应, 自由基, 水溶液, 杂环化合物

Minisci reaction is a convenient method for the functionalization of C—H in electron-defficient N-heterocycles. Different substituents could be introduced onto heterocycles through Minisci reaction, such as alkyl, acyl, silyl and alkylthio, etc. Water is eco-friendly and an ideal medium in organic synthesis, which has been applied in Minisci reaction. Recent progress in Minisci reaction in aqueous solution is reviewed herein. Minisci reaction is a convenient method for the functionalization of electron-defficient N-heterocycles. Different substituents could be introduced onto heterocycles through Minisci reaction, such as alkyl, acyl, silyl and alkylthio, boryl, etc. Thus, Minisci reaction is a powerful toolbox for the synthesis of substituted N-heterocylces. Water is eco-friendly and an ideal medium in organic synthesis, which has been applied in Minisci reaction. Although water was used from the discovery of Minisci reaction, Minisci reaction in aqueous solution is still underdeveloped. The recent progress in Minisci reaction in aqueous solution, including alkylation, arylation and acylation, is reviewed according to different radical precursors.

Key words: Minisci reaction, radical, aqueous solution, heterocycle

引用此文

王文贵, 王守锋. 水溶液中的Minisci反应研究进展[J]. 有机化学, 2024, 44(7): 2136-2146.

Wengui Wang, Shoufeng Wang. Recent Advances of Minisci Reactions in Aqueous Solution[J]. Chinese Journal of Organic Chemistry, 2024, 44(7): 2136-2146.

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图/表 32

图式1. 自由基类型的C—H键官能团化

Scheme 1. Radical-tpye C—H functionalization

图式2. 水溶液中AgNO3-(NH4)2S2O8体系促进的脱羧Minisci反应

Scheme 2. Decarboxylative Minisci reaction promoted by AgNO3-(NH4)2S2O8 in aqueous solution

图式3. 水溶液中银促进的嘧啶和羧酸的脱羧烷基化反应

Scheme 3. Decarboxylative alkylation of pyrimidines with alkyl carboxylic acids in aqueous solution

图式4. 水溶液中银催化的氮杂芳环化合物的二氟甲基化反应

Scheme 4. Silver-catalyzed difluoromethylation of heteroaromatic compounds in aqueous solution

图式5. 水溶液中银催化的氮杂芳环化合物的芳基二氟甲基化反应

Scheme 5. Silver-catalyzed difluoromethylarylation of heteroaromatic compounds in aqueous solution

图式6. 水溶液中未保护氨基酸作为自由基前体的Minisci反应

Scheme 6. Minisci reactions using unprotected amino acids as radical precursors in aqueous solution

图式7. 水溶液中Selectfluor作为氧化剂的银催化Minisci烷基化反应

Scheme 7. Silver-catalyzed Minisci reactions using Selectfluor as oxidant in aqueous solution

图式8. 水溶液中不需要外加酸的Minisci反应

Scheme 8. Minisci reactions without extrenal acid in aqueous solution

图式9. 水溶液中无过渡金属的香豆素的脱羧Minisci反应

Scheme 9. Transition metal-free decarboxylative Minisci reaction of coumarins in aqueous solution

图式10. 水溶液中草酸单酯作为自由基前体的Minisci反应

Scheme 10. Minisci reaction using oxalates as radical precursors in aqueous solution

图式11. 水溶液中可见光催化的脱羧Minisci反应

Scheme 11. Visible light-catalyzed decarboxylative Minisci rea- ction in aqueous solution

图式12. 水溶液中可见光催化的醚的芳基化反应

Scheme 12. Visible light-catalyzed arylation of ethers in aqueous solution

图式13. 水溶液中无催化剂的可见光催化醚的芳基化反应

Scheme 13. Visible light-catalyzed photocatalyst free arylation of ethers in aqueous solution

图式14. 水溶液中过硫酸盐促进醚的芳基化反应

Scheme 14. Persulfate-enabled arylation of ethers in aqueous solution

图式15. 水相中可见光催化醇的芳基化反应

Scheme 15. Visible light-catalyzed arylation of alcohols in aqueous solution

图式16. 水溶液中环状叔醇的Minisci反应

Scheme 16. Minisci reactions using tertiary cycloalkanols in aqueous solution

图式17. 水溶液中可见光催化的叔醇分子内远端C—H的杂芳基化

Scheme 17. Visible light-catalyzed heteroarylation of remote C—H in tertiary alcohols in aqueous solution

图式18. 水促进的可见光催化的醛作为烷基化试剂的Minisci反应

Scheme 18. Water-promoted visible light-catalyzed Minisci reactions using aldehydes as alkylating reagent

图式19. 水溶液中可见光催化的胺的芳基化反应

Scheme 19. Visible light-catalyzed arylation of amines in aqueous solution

图式20. 水溶液中可见光催化的氮杂芳烃的烷基化反应

Scheme 20. Visible light-catalyzed alkylation of N-heteroaro- matics in aqueous solution

图式21. 水溶液中锰(III)促进的烷基三氟硼酸钾和氮杂芳烃的Minisci反应

Scheme 21. Mn(III)-promoted Minisci reaction of alkyl trifluoroborates and N-heteroaromatics in aqueous solution

图式22. 水溶液中可见光催化的的烷基三氟硼酸钾的Minisci反应

Scheme 22. Visibile light-catalyzed Minisci reaction of alkyl trifluoroborates in aqueous solution

图式23. 水溶液中烷基二氢吡啶作为烷基化试剂的Minisci反应

Scheme 23. Minisci reactions using 1,4-dihydropyridines as alkylating reagents in aqueous solution

图式24. 水溶液中氮杂芳烃的三氟甲基化反应

Scheme 24. Trifluoromethylation of N-heteroaromatics in aqueous solution

图式25. 水溶液中氮杂芳烃的氟烷基化反应

Scheme 25. Fluoalkylation of N-heteroaromatics in aqueous solution

图式26. 水溶液中氮杂芳烃的烷基化反应

Scheme 26. Alkylation of N-heteroaromatics in aqueous solution

图式27. 水溶液中银催化的氮杂芳烃的芳基化反应

Scheme 27. Silver-catalyzed arylation of N-heteroaromatics in aqueous solution

图式28. 水相中可见光催化的Minisci芳基化反应

Scheme 28. Visible light-catalyzed Minisci-tpye arylation in aqueous solution

图式29. 水溶液中采用三氮烯的Minisci芳基化反应

Scheme 29. Minisci-tpye arylation using triazenes in aqueous solution

图式30. 水溶液中可见光催化的脱羧Minisci酰基化反应

Scheme 30. Visible light-catalyzed decarboxylative Minisci-tpye acylation in aqueous solution

图式31. 水溶液中银催化的醛和氮杂芳烃的酰基化反应

Scheme 31. Silver-catalyzed acylation of N-heteroaromatics using aldehydes in aqueous solution

图式32. 水溶液中可见光催化的炔烃和氮杂芳烃的酰基化反应

Scheme 32. Visible light-catalyzed acylation of N-heteroaro- matics using alkynes in aqueous solution

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