Progress in C—CF3/C—N Bond Formation Reactions of Alkenes Involving in Free Radicals

doi:10.6023/cjoc202208026

Abstract

Bifunctionalization of alkenes is a hot topic in organic synthesis, which can introduce different functional groups into the carbon-carbon double bond (C=C) of olefins quickly and economically, thereby increasing the complexity and application value of molecules. The trifluoromethyl groups can influence lipophilicity, permeability, and metabolic stability of organic compounds. Meanwhile, C—N bond widely exists in various organic molecules. The construction of C—CF₃/C—N bond simultaneously through bifunctionalization of alkenes is of great significant in the field of organic synthesis and medicinal chemistry. In this review, we focus on the progress in C—CF₃/C—N bond formation reactions of alkenes involving free radical intermediates based on different “N” sources. The possible radical reaction mechanism and their possible applications are also highlighted.

Key words: free radicals, alkenes, trifluoromethyl groups, C—N bond

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Lüyin Zheng, Yihan Wang, Liuhuan Cai, Wei Guo. Progress in C—CF₃/C—N Bond Formation Reactions of Alkenes Involving in Free Radicals[J]. Chinese Journal of Organic Chemistry, 2022, 42(12): 4078-4098.

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Fig. & Tab. 39

Scheme 1. C—CF3/C—N Bond formation reactions of alkenes

Scheme 2. Copper-catalyzed N-centered radical-induced aminotrifluoromethylation of alkenes

Scheme 3. Photocatalytic aminotrifluoromethylation of alkenes

Scheme 4. Precious metal-free photocatalytic aminotrifluoromethylation of alkenes

Scheme 5. Photoinduced copper-catalyzed aminotrifluoromethylation of alkenes

Scheme 6. Synergistic Lewis acid and photoredox-catalyzed aminotrifluoromethylation of alkenes

Scheme 7. Constant current electrolysis synergizing with a Lewis-acid catalysis protocol for the aminotrifluoromethylation of alkenes

Scheme 8. Metal-free electrocatalytic difunctionalization of alkene aminotrifluoromethyl

Scheme 9. Copper-catalyzed azidotrifluoromethylation of alkenes

Scheme 10. Copper-catalyzed three-component azidotrifluoromethylation of alkenes

Scheme 11. Copper-catalyzed azidotrifluoromethylation of alkenes

Scheme 12. Copper-catalyzed asymmetric azidotrifluoromethylation of acrylamides

Scheme 13. Iron-catalyzed azidotrifluoromethylation of natural products

Scheme 14. Iron-catalyzed azidotrifluoromethylation of olefins

Scheme 15. Iron-catalyzed azidotrifluoromethylation of alkenes/ alkynes

Scheme 16. Iron-catalyzed asymmetric azidotrifluoromethylation of styrenes

Scheme 17. Iron-catalyzed asymmetric azidotrifluoromethylation of styrenes

Scheme 18. Manganese-catalyzed azidotrifluoromethylation of alkenes

Scheme 19. Metal-free azidotrifluoromethylation of alkenes

Scheme 20. Photocatalytic azidotrifluoromethylation of enecarbamates

Scheme 21. Photoredox-catalyzed azidotrifluoromethylation of alkenes

Scheme 22. Photoredoxcatalyzed azidotrifluoromethylation of alkenes

Scheme 23. Photoinduced, copper-catalyzed azidotrifluoromethylation of alkenes

Scheme 24. Photocatalyzed azidotrifluoromethylation of alkenes

Scheme 25. Photocatalytic azotrifluoromethylation of alkenes

Scheme 26. Photocatalytic trifluoromethyl-hydrazination of alkenes

Scheme 27. Copper-catalyzed intramolecular aminotrifluoromethylative cyclization of allylamines

Scheme 28. Copper-catalyzed intramolecular aminotrifluoromethylative cyclization of unactivated alkenes

Scheme 29. Direct asymmetric radical aminotrifluoromethylative cyclization of enamines through a dual-catalytic strategy

Scheme 30. Catalytic asymmetric radical aminotrifluoromethlative cyclization of enamines

Scheme 31. Copper-catalyzed intramolecular aminotrifluoromethylative cyclization of enamines

Scheme 32. Copper-catalyzed trifluoromethylative cyclization of β,γ-unsaturated hydrazones

Scheme 33. Copper-catalyzed intramolecular aminotrifluoromethylative cyclization of O-homoallyl benzimidates

Scheme 34. Photocatalytic intramolecular trifluoromethylation/ cyclization of allylic amines

Scheme 35. Photocatalytic intramolecular trifluoromethylation/ cyclization of unsaturated hydrazones or oximes

Scheme 36. Photocatalytic regioselective trifluoromethylative spirocyclization of cyclic alkenes containing an amide pendant

Scheme 37. Photocatalytic three-component tandem reaction of vinylimines

Scheme 38. Electrochemical tandem trifluoromethylative cyclization of allylamines

Scheme 39. Electrochemical intramolecular trifluoromethylative cyclization of N-tethered alkenyl alcohols

References 51

[1]	Hopkins, B. A.; Wolfe, J. P. Angew. Chem., Int. Ed. 2012, 51, 9886. doi: 10.1002/anie.201205233
[2]	(a) Wu, K.; Liang, Y.; Jiao, N. Molecules 2016, 21, 352. doi: 10.3390/molecules21030352
	(b) Yin, G.; Mu, X.; Liu, G. Acc. Chem. Res. 2016, 49, 2413. doi: 10.1021/acs.accounts.6b00328
	(c) Li, Z.-L.; Fang, G.-C.; Gu, Q.-S.; Liu, X.-Y. Chem. Soc. Rev. 2020, 49, 32. doi: 10.1039/C9CS00681H
[3]	(a) Bégué, J.-P.; Bonnet-Delpon, D. J. Fluorine Chem. 2006, 12, 992. pmid: 25011917
	(b) Wu, X.-F.; Neumann, H.; Beller, M. Chem. Asian J. 2012, 7, 1744. doi: 10.1002/asia.201200211 pmid: 25011917
	(c) Zhang, C. Org. Biomol. Chem. 2014, 12, 6580. doi: 10.1039/c4ob00671b pmid: 25011917
[4]	(a) Kolahdouzan, K.; Kumar, R.; Gaunt, M. J. Chem. Sci. 2020, 11, 12089. doi: 10.1039/d0sc04853d pmid: 34094424
	(b) Duan, P.; Zhao, H.; Yang, J.; Cao, L.; Jiang, H.; Zhang, M. Org. Lett. 2022, 24, 608. doi: 10.1021/acs.orglett.1c04048 pmid: 34094424
[5]	(a) Bohm, H.-J.; Banner, D.; Bendels, S.; Kansy, M.; Kuhn, B.; Muller, K.; Obst-Sander, U.; Stahl, M. ChemBioChem 2004, 5, 637. doi: 10.1002/cbic.200301023 pmid: 25727703
	(b) Kirk, K. L. J. Fluorine Chem. 2006, 127, 1013. doi: 10.1016/j.jfluchem.2006.06.007 pmid: 25727703
	(c) Swallow, S. Prog. Med. Chem. 2015, 54, 65. doi: 10.1016/bs.pmch.2014.11.001 pmid: 25727703
[6]	(a) Yu, J.; Zhou, Y.; Chen, D.-F.; Gong, L.-Z. Pure Appl. Chem. 2014, 86, 1217. doi: 10.1515/pac-2013-1208
	(b) Suliman, R. S.; Alghamdi, S. S.; Ali, R.; Rahman, I.; Alqahtani, T.; Frah, I. K.; Aljatli, D. A.; Huwaizi, S.; Algheribe, S.; Alehaideb, Z.; Islam, I. Molecules 2022, 27, 2409. doi: 10.3390/molecules27082409
	(c) Sasidharan, N.; Kumar, A. S.; Hng, H. H. ChemistrySelect 2018, 3, 12544. doi: 10.1002/slct.201803239
[7]	Chen, X.; Xiao, F.; He, W.-M. Org. Chem. Front. 2021, 8, 5206. doi: 10.1039/D1QO00375E
[8]	(a) Egami, H.; Sodeoka, M. Angew. Chem., Int. Ed. 2014, 53, 8294. doi: 10.1002/anie.201309260
	(b) Merino, E.; Nevado, C. Chem. Soc. Rev. 2014, 43, 6598. doi: 10.1039/C4CS00025K
[9]	Koike, T. Asian J. Org. Chem. 2020, 9, 529. doi: 10.1002/ajoc.202000058
[10]	(a) Chen, D.; Yang, W.; Yao, Y.; Yang, X.; Deng, Y.; Yang, D. Chin. J. Org. Chem. 2018, 38, 2571. (in Chinese) doi: 10.6023/cjoc201803045
	( 陈董涵, 杨文, 姚永祺, 杨新, 邓颖颖, 杨定乔, 有机化学, 2018, 38, 2571.) doi: 10.6023/cjoc201803045
	(b) Qiu, Y.; Wei, F.; Ye, L.; Zhao, M. Chin. J. Org. Chem. 2021, 41, 1821. (in Chinese)
	( 邱云亮, 魏凤姣, 叶鎏, 赵旻玥, 有机化学, 2021, 41, 1821.) doi: 10.6023/cjoc202009036
[11]	Xiao, H.; Shen, H.; Zhu, L.; Li, C. J. Am. Chem. Soc. 2019, 141, 11440. doi: 10.1021/jacs.9b06141
[12]	(a) Guo, W.; Tao, K.; Tan, W.; Zhao, M.; Zheng, L.; Fan, X. Org. Chem. Front. 2019, 6, 2048. doi: 10.1039/C8QO01353E
	(b) Zheng, L.; Cai, L.; Tao, K.; Xie, Z.; Lai, Y.-L.; Guo, X. Asian J. Org. Chem. 2021, 10, 711. doi: 10.1002/ajoc.202100009
	(c) Zheng, L.; Tao, K.; Guo, W. Adv. Synth. Catal. 2021, 363, 62. doi: 10.1002/adsc.202001079
[13]	Yasu, Y.; Koike, T.; Akita, M. Org. Lett. 2013, 15, 2136. doi: 10.1021/ol4006272
[14]	Noto, N.; Koike, T.; Akita, M. Chem. Sci. 2017, 8, 6375. doi: 10.1039/C7SC01703K
[15]	Xiong, Y.; Ma, X.; Zhang, G. Org. Lett. 2019, 21, 1699. doi: 10.1021/acs.orglett.9b00252 pmid: 30802073
[16]	Ge, H.; Wu, B.; Liu, Y.; Wang, H.; Shen, Q. ACS Catal. 2020, 10, 12414. doi: 10.1021/acscatal.0c03776
[17]	Zhang, L.; Zhang, G.; Wang, P.; Li, Y.; Lei, A. Org. Lett. 2018, 20, 7396. doi: 10.1021/acs.orglett.8b03081
[18]	Huang, Y.; Hong, H.; Zou, Z.; Liao, C.; Lu, J.; Qin, Y.; Li, Y.; Chen, L. Org. Biomol. Chem. 2019, 17, 5014. doi: 10.1039/C9OB00717B
[19]	Wang, F.; Qi, X.; Liang, Z.; Chen, P.; Liu, G. Angew. Chem., Int. Ed. 2014, 53, 1881. doi: 10.1002/anie.201309991
[20]	Yang, M.; Wang, W.; Liu, Y.; Feng, L.; Ju, X. Chin. J. Chem. 2014, 32, 833. doi: 10.1002/cjoc.201400167
[21]	Xiong, Y.; Sun, Y.; Zhang, G. Org. Lett. 2018, 20, 6250. doi: 10.1021/acs.orglett.8b02735 pmid: 30246540
[22]	Wu, L.; Zhang, Z.; Wu, D.; Wang, F.; Chen, P.; Lin, Z.; Liu, G. Angew. Chem., Int. Ed. 2021, 60, 6997. doi: 10.1002/anie.202015083
[23]	Karimov, R. R.; Sharma, A.; Hartwig, J. F. ACS Cent. Sci. 2016, 2, 715. doi: 10.1021/acscentsci.6b00214
[24]	Zhu, C.-L.; Wang, C.; Qin, Q.-X.; Yruegas, S.; Martin, C. D.; Xu, H. ACS Catal. 2018, 86, 5032.
[25]	Xiong, H.; Ramkumar, N.; Chiou, M.-F.; Jian, W.; Li, Y.; Su, J.-H.; Zhang, X.; Bao, H. Nat. Commun. 2019, 10, 122. doi: 10.1038/s41467-018-07985-2
[26]	Ge, L.; Zhou, H.; Chiou, M.-F.; Jiang, H.; Jian, W.; Ye, C.; Li, X.; Zhu, X.; Xiong, H.; Li, Y.; Song, L.; Zhang, X.; Bao, H. Nat. Catal. 2021, 4, 28. doi: 10.1038/s41929-020-00551-4
[27]	Liu, W.; Pu, M.; He, J.; Zhang, T.; Dong, S.; Liu, X.; Wu, Y.-D.; Feng, X. J. Am. Chem. Soc. 2021, 143, 11856. doi: 10.1021/jacs.1c05881
[28]	Zhang, Y.; Han, X.; Zhao, J.; Qian, Z.; Li, T.; Tang, Y.; Zhang, H.-Y. Adv. Synth. Catal. 2018, 360, 2659. doi: 10.1002/adsc.201800488
[29]	Huang, H.-G.; Li, W.; Zhong, D.; Wang, H.-C.; Zhao, J.; Liu, W.-B. Chem. Sci. 2021, 12, 3210. doi: 10.1039/D0SC06473D
[30]	Carboni, A.; Dagousset, G.; Magnier, E.; Masson, G. Org. Lett. 2014, 16, 1240. doi: 10.1021/ol500374e pmid: 24520865
[31]	Dagousset, G.; Carboni, A.; Magnier, E.; Masson, G. Org. Lett. 2014, 16, 4340. doi: 10.1021/ol5021477
[32]	Geng, X.; Lin, F.; Wang, X.; Jiao, N. Org. Lett. 2017, 19, 4738. doi: 10.1021/acs.orglett.7b02056
[33]	Liu, H.; Guo, Q.; Chen, C.; Wang, M.; Xu, Z. Org. Chem. Front. 2018, 5, 1522. doi: 10.1039/C8QO00120K
[34]	Zhang, M.; Lin, J.-H.; Xiao, J.-C. Org. Lett. 2021, 23, 6079. doi: 10.1021/acs.orglett.1c02146
[35]	Yu, X.-L.; Chen, J.-R.; Chen, D.-Z.; Xiao, W.-J. Chem. Commun. 2016, 52, 8275. doi: 10.1039/C6CC03335K
[36]	Wang, P.; Zhu, S.; Lu, D.; Gong, Y. Org. Lett. 2020, 22, 1924. doi: 10.1021/acs.orglett.0c00287
[37]	Egami, H.; Kawamura, S.; Miyazaki, A.; Sodeoka, M. Angew. Chem., Int. Ed. 2013, 52, 7841. doi: 10.1002/anie.201303350
[38]	Lin, J.-S.; Xiong, Y.-P.; Ma, C.-L.; Zhao, L.-J.; Tan, B.; Liu, X.-Y. Chem.-Eur. J. 2014, 20, 1332. doi: 10.1002/chem.201303387
[39]	Lin, J.-S.; Dong, X.-Y.; Li, T.-T.; Jiang, N.-C.; Tan, B.; Liu, X.-Y. J. Am. Chem. Soc. 2016, 138, 9357. doi: 10.1021/jacs.6b04077
[40]	Lin, J.-S.; Wang, F.-L.; Dong, X.-Y.; He, W.-W.; Yuan, Y.; Chen, S.; Liu, X.-Y. Nat. Commun. 2017, 8, 14841. doi: 10.1038/ncomms14841
[41]	Zhang, H.-Y.; Huo, W.; Ge, C.; Zhao, J.; Zhang, Y. Synlett 2017, 28, 962. doi: 10.1055/s-0036-1588400
[42]	Chang, B.; Su, Y.; Huang, D.; Wang, K.-H.; Zhang, W.; Shi, Y.; Zhang, X.; Hu, Y. J. Org. Chem. 2018, 83, 4365. doi: 10.1021/acs.joc.8b00009
[43]	Mou, X.-Q.; Rong, F.-M.; Zhang, H.; Chen, G.; He, G. Org. Lett. 2019, 21, 4657. doi: 10.1021/acs.orglett.9b01552
[44]	Kim, E.; Choi, S.; Kim, H.; Cho, E. J. Chem.-Eur. J. 2013, 19, 6209. doi: 10.1002/chem.201300564
[45]	Wei, Q.; Chen, J.-R.; Hu, X.-Q.; Yang, X.-C.; Lu, B.; Xiao, W.-J. Org. Lett. 2015, 17, 4464. doi: 10.1021/acs.orglett.5b02118
[46]	Noto, N.; Miyazawa, K.; Koike, T.; Akita, M. Org. Lett. 2015, 17, 3710. doi: 10.1021/acs.orglett.5b01694
[47]	Jarrige, L.; Carboni, A.; Dagousset, G.; Levitre, G.; Magnier, E.; Masson, G. Org. Lett. 2016, 18, 2906. doi: 10.1021/acs.orglett.6b01257 pmid: 27276522
[48]	Claraz, A.; Djian, A.; Masson, G. Org. Chem. Front. 2021, 8, 288. doi: 10.1039/D0QO01307B
[49]	Claraz, A.; Courant, T.; Masson, G. Org. Lett. 2020, 22, 1580. doi: 10.1021/acs.orglett.0c00176
[50]	Zheng, Y.-N.; Zheng, H.; Li, T.; Wei, W.-T. ChemSusChem 2021, 14, 5340. doi: 10.1002/cssc.202102243
[51]	Proctor, P. S. J.; Colgan, A. C.; Phipps, R. J. Nat. Chem. 2020, 12, 990. doi: 10.1038/s41557-020-00561-6 pmid: 33077927

自由基参与的烯烃C—CF₃/C—N键形成反应研究进展

Progress in C—CF₃/C—N Bond Formation Reactions of Alkenes Involving in Free Radicals

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自由基参与的烯烃C—CF3/C—N键形成反应研究进展