芳烃三氟甲基断裂单碳氟键的反应研究进展

doi:10.6023/cjoc202110037

有机化学 ›› 2021, Vol. 41 ›› Issue (12): 4554-4564.DOI: 10.6023/cjoc202110037 上一篇下一篇

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综述与进展

芳烃三氟甲基断裂单碳氟键的反应研究进展

安辛妮^a, 冯璋^b, 黄林^a, 杨义^a^,^*(), 刘正立^b^,^*()

a 四川轻化工大学化学与环境工程学院四川自贡 643000
b 重庆大学药学院重庆 401331

收稿日期:2021-10-25 修回日期:2021-11-30 发布日期:2021-12-08
通讯作者: 杨义, 刘正立
基金资助:
国家自然科学基金(21801029); 重庆博士后科学基金(cstc2019jcyj-bshx0057); 中国博士后科学基金(2020M673121); 四川省教育厅(18CZ0024); 钒钛资源综合利用四川省重点实验室(2018FTSZ03); 大学生创新创业训练计划(S202010622050)

Recent Advances in the Single C—F Bond Cleavage Reactions of Trifluoromethylarenes

Xinni An^a, Zhang Feng^b, Lin Huang^a, Yi Yang^a(), Zhengli Liu^b()

a College of Chemistry and Environmental Engineering, Sichuan University of Science and Engineering, Zigong, Sichuan 643000
b School of Pharmaceutical Sciences, Chongqing University, Chongqing 401331

Received:2021-10-25 Revised:2021-11-30 Published:2021-12-08
Contact: Yi Yang, Zhengli Liu
Supported by:
National Natural Science Foundation of China(21801029); Chongqing Postdoctoral Science Foundation(cstc2019jcyj-bshx0057); China Postdoctoral Science Foundation(2020M673121); Education Department of Sichuan Province(18CZ0024); Key Laboratory of Vanadium and Titanium of Sichuan Province(2018FTSZ03); College Students’ Innovation and Entrepreneurship Training Program(S202010622050)

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摘要/Abstract

芳烃三氟甲基化合物价廉易得, 通过对其C(sp³)—F键进行选择性切断是合成含偕二氟基团医药中间体的重要途径. 然而, 该转化中面临着巨大挑战, 如C(sp³)—F键难以活化, 以及如何实现选择性脱单氟键等问题. 近年来该领域发展迅速, 取得了一系列重要的研究成果. 如通过对三氟甲基的转化, 开发出了构建偕二氟烷基基团的简洁而高效的方法,其中涉及二氟烷基自由基或二氟甲基碳阳离子中间体. 根据ArCF₃选择性切断单C(sp³)—F键的策略进行分类, 对该领域最新研究进展进行了概述.

关键词: 选择性碳氟键切断, 芳烃三氟甲基, 二氟烷基自由基

Trifluoromethylarene compounds are readily available, and the highly selective cleavage of one C(sp³)—F bond in trifluoromethyl group is an important strategy to access pharmaceutical molecules containing the gem-difluoro groups. However, there are still some challenges in this field, such as the difficulty in activating the C(sp³)—F bond and the highly selective cleavage of the single C(sp³)—F bond. In recent years, efficient methods for the construction of gem-difluoro groups have been developed through the transformation of trifluoromethyl group, in which difluoroalkyl radicals or difluoromethyl carbocation intermediates are alway involved. The recent research progress in this field is summarized based on the cleavage strategies of trifluoromethyl group.

Key words: selective cleavage of C—F bond, trifluoromethylarenes, difluoroalkyl radical

引用此文

安辛妮, 冯璋, 黄林, 杨义, 刘正立. 芳烃三氟甲基断裂单碳氟键的反应研究进展[J]. 有机化学, 2021, 41(12): 4554-4564.

Xinni An, Zhang Feng, Lin Huang, Yi Yang, Zhengli Liu. Recent Advances in the Single C—F Bond Cleavage Reactions of Trifluoromethylarenes[J]. Chinese Journal of Organic Chemistry, 2021, 41(12): 4554-4564.

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图/表 19

图式1. 光催化三氟甲基芳烃与丙烯酰胺的成环反应

Scheme 1. Photocatalytic ring-forming reaction of trifluoromet-hylarenes and acrylamides

图式2. 三氟甲基芳烃与未活化烯烃的可控脱氟烷基化-末端官能团化反应

Scheme 2. Controllable defluoroalkylation-distal functionalization of trifluoromethylarenes with unactivated alkenes

图式3. 可见光催化下C(sp3)—F键与CO2的选择性羧基化反应

Scheme 3. Visible-light photoredox-catalyzed selective carboxylation of C(sp3)—F bonds with CO2

图式4. 光催化三氟甲基芳烃与未活化烯烃的脱氟烷基化反应

Scheme 4. Photocatalytic defluoroalkylation of trifluoromethylarenes with unactivated alkenes

图式5. COF作为光催化剂实现三氟甲基芳烃与烯烃的脱氟烷基化反应

Scheme 5. The defluoroalkylation of trifluoromethylarenes with alkenes using COF as photocatalysts

图式6. 光催化三氟甲基芳烃的脱氟烷基化和脱氟氢化反应

Scheme 6. Photocatalytic defluoroalkylation and defluorohydrogenation of trifluoromethylarenes

图式7. 未活化三氟甲基芳烃的选择性C—F键官能团化反应

Scheme 7. Selective C—F bond functionalization of unactivated trifluoromethylarenes

图式8. 可能的反应机理

Scheme 8. Possible reaction mechanism

图式9. 三氟乙酰胺或乙酸酯通过SCS的氟取代反应

Scheme 9. Fluorine substitution reaction of trifluoroacetamides or acetates via SCS

图式10. 三氟甲基芳烃与芳基硼酸的偶联

Scheme 10. Coupling of trifluoromethylarenes and arylboric acids

图式11. 可能的反应机理

Scheme 11. Proposed reaction mechanism

图式12. Sc(OTf)3催化活化三氟甲基中的单C—F键

Scheme 12. Sc(OTf)3-catalyzed activation of single C—F bond in CF3 group

图式13. 具有邻位氢硅基的三氟甲基芳烃的单C—F键裂解及其烯丙基化

Scheme 13. Single C—F bond cleavage and allylation of trifluoromethylarenes bearing a hydrosilyl group at the ortho position

图式14. 三氟甲基芳烃的选择性单氟取代反应

Scheme14. Selective single fluoride substitution reaction in trifluoromethylarenes

图式15. Pd/Cu共催化三氟甲基芳烃单C—F键还原氢化

Scheme 15. Pd/Cu catalyzed single C—F bond reductive hydrogenation of trifluoromethylarenes

图式16. 光催化三氟甲基芳烃的脱氟氢化

Scheme 16. Organophotoredox hydrodefluorination of trifluoromethylarenes

图式17. 三氟甲基芳烃转化为具有生物活性的二氟甲基芳烃衍生物

Scheme 17. Conversion of trifluoromethylarenes into biologically active difluoromethylarene derivatives

图式18. 三氟甲基芳烃中单C(sp3)—F键与零价镍配合物的氧化加成

Scheme 18. The oxidative addition of a C(sp3)—F bond in trifluoromethylarenes with nickel(0) complex

图式19. 三氟乙酰胺和三氟乙酸酯的连续C—F键还原氢化反应

Scheme 19. Sequential C—F bond reductive hydrogenation of trifluoroacetamides and acetates

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芳烃三氟甲基断裂单碳氟键的反应研究进展

Recent Advances in the Single C—F Bond Cleavage Reactions of Trifluoromethylarenes

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