氟烷基羧酸的脱羧氟烷基化反应研究进展

doi:10.6023/cjoc202208017

摘要/Abstract

氟烷基羧酸衍生物的脱羧反应是获得氟烷基自由基的有效途径, 而该自由基物种参与烯烃、异腈以及芳(杂)环的串联、加成反应是获取各种含氟官能化有机分子的重要方法. 通过氟烷基羧酸产生的氟烷基自由基引发的串联反应可以构建啡啶、二氢黄酮、喹啉-2,4-二酮及吲哚酮等环状骨架. 综述了近年来氟烷基羧酸脱羧引发的自由基反应的研究进展, 涵盖反应设计、反应机理及研究展望等内容.

关键词: 氟烷基化, 脱羧反应, 羧酸

Decarboxylation of fluoroalkyl carboxylic acid derivatives is an effective way to obtain fluoroalkyl radicals, which subsequently participates in the tandem and addition reactions of olefins, isonitriles and aromatic (hetero) rings, providing an important method to obtain divegent fluorine-containing molecules. A variety of fluoroalkyl cyclic compounds such as phenanthridines, dihydroflavonoid, quinolinones and indolones could be constructed using the tandem reaction initiated by fluoroalkyl radicals generated from fluoroalkyl carboxylic acids. The research progress of radical reactions induced by decarboxylation of fluoroalkyl carboxylic acids in recent years is summarized, which includes reaction design, reaction mechanism and outlook.

Key words: fluoroalkylation, decarboxylative reaction, carboxylic acid

引用此文

朱玉溪, 肖婷, 夏冬, 杨文超. 氟烷基羧酸的脱羧氟烷基化反应研究进展[J]. 有机化学, 2022, 42(12): 4067-4077.

Yuxi Zhu, Ting Xiao, Dong Xia, Wenchao Yang. Recent Advances in the Decarboxylative Fluoroalkylation of Fluoroalkyl Carboxylic Acids[J]. Chinese Journal of Organic Chemistry, 2022, 42(12): 4067-4077.

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图/表 20

图式1. 氟烷基羧酸脱羧引发不饱和烃的自由基串联反应

Scheme 1. Radical cascade reaction of unsaturated hydrocarbon initiated by decarboxylation of fluoroalkyl carboxylic acids

图式2. 合成6-偕二氟亚甲基菲啶

Scheme 2. Synthesis of 6-gem-difluoromethylenated phenanthridine

图式3. 二氟氧化吲哚与硫代二氟氧化吲哚衍生物的合成

Scheme 3. Synthesis of difluorooxindoles and thiodifluorooxindole derivatives

图式4. 二氟喹啉酮衍生物的合成

Scheme 4. Synthesis of difluoroquinolinone derivatives

图式5. 二氢黄酮与茚满酮的合成

Scheme 5. Synthesis of chroman-4-ones and indanones

图式6. 喹唑啉酮衍生物的合成

Scheme 6. Synthesis of quinazolinone derivatives

图式7. 银催化芳烃的三氟甲基化

Scheme 7. Silver-catalyzed C—H trifluoromethylation of arenes

图式8. 杂芳烃的二氟甲基化

Scheme 8. Difluoromethylation of heteroarenes

图式9. 银催化杂芳烃的一氟甲基化

Scheme 9. Silver-catalyzed monofluoroalkylation of heteroarenes

图式10. 喹喔啉酮的偕-芳基二氟甲基化

Scheme 10. gem-Aryldifluoromethylation of quinoxalin-2(1H)- ones

图式11. 银催化氮芳杂环的偕-芳基二氟甲基化

Scheme 11. Ag-catalyzed gem-aryldifluoromethylation of N- heteroarenes

图式12. 喹啉氮氧化物的偕-芳基二氟甲基化

Scheme 12. gem-Aryldifluoromethylation of quinoline N-oxides

图式13. 香豆素的偕-芳基二氟甲基化与芳硫基二氟甲基化

Scheme 13. gem-Aryldifluoromethylation and arylthiodifluoromethylation of coumarins

图式14. 钯催化脱羧间位C—H偕-芳基二氟甲基化

Scheme 14. Pd-catalyzed decarboxylative meta-C—H difluoromethylation

图式15. α,α-二氟芳基乙酸的催化脱羧氟化反应

Scheme 15. Catalytic decarboxylative fluorination of α,α-difluoroarylacetic acids

图式16. α,α-二氟芳基乙酸的脱羧炔基化反应

Scheme 16. Decarboxylative alkynylation of α,α-difluoroarylacetic acids

图式17. α,α-二氟芳基乙酸的脱羧烷基化与巯基化反应

Scheme 17. Decarboxylative alkylation and thiolation of α,α-difluoroarylacetic acids

图式18. α,α-二氟芳基乙酸的脱羧烷基化反应

Scheme 18. Decarboxylative alkylation of α,α-difluoro- arylacetic acids

图式19. 烯烃与α,α-二氟芳基乙酸的氢芳基二氟甲基化

Scheme 19. Hydroaryldifluoromethylation of alkenes with α,α-difluoroarylacetic acids

图式20. 烯烃与α-氟代羧酸的氢芳基二氟甲基化

Scheme 20. Hydroaryldifluoromethylation of alkenes with α-fluoro carboxylic acids

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