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

doi:10.6023/cjoc202110037

Chinese Journal of Organic Chemistry ›› 2021, Vol. 41 ›› Issue (12): 4554-4564.DOI: 10.6023/cjoc202110037 Previous Articles Next Articles

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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)

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

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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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Fig. & Tab. 19

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

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

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

Scheme 4. Photocatalytic defluoroalkylation of trifluoromethylarenes with unactivated alkenes

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

Scheme 6. Photocatalytic defluoroalkylation and defluorohydrogenation of trifluoromethylarenes

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

Scheme 8. Possible reaction mechanism

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

Scheme 10. Coupling of trifluoromethylarenes and arylboric acids

Scheme 11. Proposed reaction mechanism

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

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

Scheme14. Selective single fluoride substitution reaction in trifluoromethylarenes

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

Scheme 16. Organophotoredox hydrodefluorination of trifluoromethylarenes

Scheme 17. Conversion of trifluoromethylarenes into biologically active difluoromethylarene derivatives

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

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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Fig. & Tab. 19

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