过渡金属催化碳氢键活化合成烷基氟烷基化合物的研究进展

doi:10.6023/cjoc202406033

摘要/Abstract

过渡金属催化碳氢键活化是人们研究的热点领域之一. 通过碳氢键断裂合成有机氟化合物是一种直接、高效的合成方法. 相对于芳基/炔基取代氟烷基化合物的合成, 过渡金属催化烷基氟烷基化合物(C(sp³)-R_f)的合成相对比较滞后. 此文主要介绍了近些年过渡金属(铑、钌、钯、铜、铱、镍和锰等)催化碳氢键(sp²或sp³ C—H键)活化合成烷基氟烷基化合物的研究进展, 最后总结了近期出现的几例利用碳氢键活化合成手性含氟化合物的方法.

关键词: 碳氢键活化, 过渡金属催化, 烷基氟烷基化合物

Transition-metal catalyzed insert C—H bond activation has gained great attention for the last decades, which would provide a straightforward and attractive strategy for the synthesis of organofluorine compounds. Compared with aryl and alkynyl fluoroalkyl compounds, the synthesis of C(sp³)-fluoroalkyl compounds through C—H bond activation still lag behind. This review highlights the recent advances in the synthesis of alkyl fluoroalkyl compounds through the transition-metal (Rh, Ru, Pd, Cu, Ir, Ni, Mn, etc.) catalyzed C—H bond activation. The very recently developed chiral fluorinated compound synthesis through asymmetric C—H bond activation is included.

Key words: C—H bond activation, transition-metal catalyst, C(sp³)-fluoroalkyl compounds

引用此文

王曼曼, 习文慧, 吴昊, 白大昌. 过渡金属催化碳氢键活化合成烷基氟烷基化合物的研究进展[J]. 有机化学, 2025, 45(2): 516-530.

Manman Wang, Wenhui Xi, Hao Wu, Dachang Bai. Recent Advances in Transition-Metal Catalyzed C—H Bond Activation for the Synthesis of C(sp³)-Fluoroalkyl Compounds[J]. Chinese Journal of Organic Chemistry, 2025, 45(2): 516-530.

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图/表 32

图式1. 碳氢键活化的几种常见策略

Scheme 1. Types of established C—H bond activation mechanisms

图式2. 过渡金属催化碳氢键活化合成烷基氟烷基化合物

Scheme 2. Transition-metal catalyzed C—H bond activation for the synthesis of C(sp3)-fluoroalkyl containing compounds

图式3. 铑(III)催化1-芳基-2,2,2-三氟重氮乙烷的成环反应

Scheme 3. Rh(III)-catalyzed cyclization reaction of 1-aryl-2,2,2-trifluorodiazoethanes

图式4. 铑(III)催化芳烃与三氟甲基重氮乙酸甲酯的偶联反应

Scheme 4. Rh(III)-catalyzed coupling reaction of arenes with methyl 2-diazo-3,3,3-trifluoropropanoate

图式5. 铑(III)催化三氟甲基丙烯酸酯对酰胺类底物的烯化反应

Scheme 5. Rh(III)-catalyzed olefination of carboxamides with trifluoromethyl allylic carbonate

图式6. 铑催化苯甲酰胺与α-三氟甲基丙烯酸的偶联反应

Scheme 6. Rh(III)-catalyzed coupling reaction of α-trifluoromethylacrylic acid with benzamides

图式7. 铑(III)催化C(sp2)—H键活化后与β-三氟甲基取代不饱和酮的加成反应

Scheme 7. Rhodium(III)-catalyzed C(sp2)—H bond activation and coupling with β-CF3-substituted enones

图式8. 铑催化偕二氟乙烯基甲苯磺酸盐的加成及环化反应

. Schem 8 Rhodium(III)-catalyzed addition and cyclization reaction of gem-difluorovinyl tosylate

图式9. 铑(III)-催化芳烃与偕二氟亚甲基炔烃的偶联反应

Scheme 9. Rh(III)-catalysed C—H couplings of arenes with gem-difluoromethylene alkynes

图式10. 钌(II)催化芳基硝酮的碳氢键活化及与全氟烷基烯烃的偶联反应

Scheme 10. Ru(II)-catalyzed C—H activation of aryl nitrones and coupling with perfluoroalkylolefins

图式11. 镍催化芳烃的碳氢键三氟乙基化反应

Scheme 11. Nickel catalyzed C—H trifluoroethylation of arenes

图式12. 镍催化吲哚的直接碳氢三氟乙基化反应

Scheme 12. Nickel-catalyzed direct C—H trifluoroethylation of indoles

图式13. 铜催化喹喔啉酮与六氟异丙醇的选择性C—H官能团化反应

Scheme 13. Copper-catalyzed chemoselective C—H functionalization of quinoxalin-2(1H)-ones with hexafluoroisopropanol

图式14. 铜催化环状烯烃的三氟甲基化反应

Scheme 14. Copper-catalyzed trifluoromethylation of unactivated cycloalkenes

图式15. 铜催化四氢异喹啉C(sp3)—H键活化氧化三氟甲基化反应

Scheme 15. Copper-catalyzed oxidative trifluoromethylation of benzylic sp3 C—H of tetrahydroisoquinoline derivatives

图式16. 铜催化苯酚化合物苄基C—H键的三氟甲基化反应

Scheme 16. Copper-catalyzed benzylic C—H trifluoromethylation of phenol derivatives

图式17. 铜催化苄基C(sp3)—H键的三氟甲基化

Scheme 17. Copper-mediated trifluoromethylation of benzylic C(sp3)—H bonds

图式18. 铜催化苄基C(sp3)—H三氟甲基化反应

Scheme 18. Copper-catalyzed C(sp3)—H trifluoromethylation of benzyl substrates

图式19. 铜催化烷烃的C(sp3)—H三氟甲基化反应

Scheme 19. Copper-catalyzed C(sp3)—H trifluoromethylation of alkanes

图式20. 十钨酸盐和铜催化协同光作用下实现C(sp3)—H键的三氟甲基化

Scheme 20. Merger of decatungstate photocatalysis with copper catalysis to enable aliphatic C(sp3)—H trifluoromethylation

图式21. 铜催化自由基加成的C(sp3)—H键官能团化

Scheme 21. Copper(II)-catalyzed radical trifluoroethylation through the C(sp3)—H functionalization

图式22. 铜催化烯丙基碳氢键活化合成烯丙基三氟甲基化合物

Scheme 22. Copper-catalyzed allyl C—H bond activation for the synthesis of allyl trifluoromethyl compounds

图式23. 铜催化3-芳基-1-丙炔的C—H三氟甲基化反应

Scheme 23. Cu-catalyzed C—H trifluoromethylation of 3-arylprop-1-ynes

图式24. 锰催化C(sp3)—H键的过氧官能团化反应

Scheme 24. Mn-catalyzed C(sp3)—H bond peroxidation

图式25. 铜催化氯代酰胺的苄基C—H键的二氟甲基化

Scheme 25. Copper-catalyzed chloroamide-directed benzylic C—H difluoromethylation

图式26. 钯催化C(sp3)—H键活化的三氟乙基化反应

Scheme 26. Pd-catalyzed C(sp3)—H trifluoroethylation

图式27. 钯催化烷烃碳氢键的乙氧基化反应

Scheme 27. Palladium-catalyzed ethoxylation of aliphatic C—H bond

图式28. (R)-CpRh催化芳烃C—H键和三氟丙酮酸乙酯的不对称加成反应

Scheme 28. (R)-CpRh-catalyzed asymmetric addition of C—H bond to ethyl trifluoropyruvate

图式29. 手性Rh(III)催化芳烃和烯烃碳氢键活化的不对称三氟甲基化反应

Scheme 29. chiral Rh(III) catalyzed the asymmetric trifluoromethyl alkylation reaction of aryl C—H bond

图式30. 铑催化C(sp3)—H键对卡宾的不对称插入反应

Scheme 30. Rh-catalyzed asymmetric insertion of fluoroalkyl carbene into ether α-C(sp3)—H bonds

图式31. Ir催化N-甲基C—H键和α-三氟甲基苯乙烯的不对称加成反应

Scheme 31. Ir-catalyzed asymmetric addition of N-methyl C—H bond to α-trifluoromethylstyrenes

图式32. 铜催化苄基C—H键的不对称三氟甲基化反应

Scheme 32. Cu-catalyzed asymmetric benzylic C—H trifluoromethylation

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