三氟甲硫基自由基引发不饱和烃的串联反应

doi:10.6023/cjoc202203041

摘要/Abstract

含氟有机化合物因其特殊的物理与化学性能, 在医药和农药等学科中被广泛应用, 这就促使含氟官能团经常被引入到先导化合物中以改善其理化性能. 三氟甲硫基官能团在众多含氟化合物中具有重要的地位, 因为他们具有高电负性和特殊的亲脂性. 因此, 向化合物中引入三氟甲硫基在有机氟化学领域备受关注. 综述了近年来三氟甲硫基自由基引发不饱和烃的串联反应的研究进展, 涵盖反应设计、反应机理和研究展望等内容.

关键词: 三氟甲硫基化, 不饱和烃, 串联反应, 自由基, 双官能化

Fluorinated compounds have been widely used in pharmaceuticals, pesticides and other disciplines due to their special physical and chemical properties, which motivates the frequent introduction of fluorinated functionalities into lead compounds to improve their physical and chemical properties. The trifluoromethylthio (SCF₃) group with high electronegativity and special lipophilicity plays an important role in a multitude of fluorinated compounds. The recent progress in the field of cascade reaction of unsaturated hydrocarbon initiated by SCF₃ radical, including reaction design, reaction mechanism and outlook, is summarized.

Key words: trifluoromethylthiolation, unsaturated hydrocarbon, cascade reaction, radical, difunctionalization

引用此文

石云, 肖婷, 夏冬, 杨文超. 三氟甲硫基自由基引发不饱和烃的串联反应[J]. 有机化学, 2022, 42(9): 2715-2727.

Yun Shi, Ting Xiao, Dong Xia, Wenchao Yang. SCF₃ Radical Initiated Cascade Reaction of Unsaturated Hydrocarbon[J]. Chinese Journal of Organic Chemistry, 2022, 42(9): 2715-2727.

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图/表 22

图式1. 三氟甲硫基自由基引发的不饱和烃的串联反应

Scheme 1. SCF3 radical initiated cascade reaction of unsaturated hydrocarbon

图式2. 三氟甲硫基化的氧化吲哚的合成

Scheme 2. Synthesis of trifluoromethylthiolated oxindoles

图式3. 三氟甲硫基化的吲哚[2,1-a]异喹啉与喹啉酮的合成

Scheme 3. Synthesis of trifluoromethylthiolated [2,1-a]isoquinolines and quinolinones

图式4. 可见光促进烯烃的三氟甲硫基化反应

Scheme 4. Visible-light-promoted trifluoromethylthiolation of olefins

图式5. 亚甲基环丙烷的三氟甲硫基化反应

Scheme 5. Trifluoromethylthiolation of methylenecyclopropanes

图式6. 三氟甲硫基化的苯并咪唑[2,1-a]异喹啉的合成

Scheme 6. Synthesis of SCF3-substituted benzimidazole[2,1-a]isoquinolines

图式7. 三氟甲硫基化的色胺酮的合成

Scheme 7. Synthesis of SCF3-substituted tryptanthrins

图式8. 三氟甲硫基化的茚酮的合成

Scheme 8. Synthesis of trifluoromethylthiolated indenones

图式9. 三氟甲硫基化的硫代黄酮与苯并噻唑的合成

Scheme 9. Synthesis of trifluoromethylthiolated thioflavones and benzothiophenes

图式10. 1,6-烯炔的三氟甲硫基化/自由基环化反应

Scheme 10. Trifluoromethylthiolation/radical cyclization of 1,6-enynes

图式11. 三氟甲硫基化的香豆素的合成

Scheme 11. Synthesis of trifluoromethylthiolated coumarins

图式12. 合成三氟甲硫基化的螺[4,5]三烯酮

Scheme 12. Synthesis of trifluoromethylthiolated spiro[4,5]trienones

图式13. N-[(3-芳基)丙酰基]吲哚的三氟甲硫基化反应

Scheme 13. Trifluoromethylthiolation of N-[(3-aryl)propioloyl]indoles

图式14. 联苯的电化学三氟甲硫基化

Scheme 14. Electrochemical trifluoromethylthiolation

图式15. 乙烯基三氟甲基硫醚的合成

Scheme 15. Synthesis of vinyl trifluoromethyl thioethers

图式16. 乙烯基三氟甲基硫醚的合成

Scheme 16. Synthesis of vinyl trifluoromethyl thioethers

图式17. 乙烯基三氟甲基硫醚与α-三氟甲硫基苯乙酮的合成

Scheme 17. Synthesis of vinyl trifluoromethyl thioethers and α-trifluoromethylthio acetophenons

图式18. 非活化烯烃和炔烃与三氟甲磺酸酐的氢三氟甲基硫基化反应

Scheme 18. Hydrotrifluoromethylthiolative reaction of unactivated alkenes and alkynes with trifluoromethanesulfonic anhydride

图式19. 光催化炔烃的自由基三氟甲硫基化-硼化反应

Scheme 19. Photocatalyzed radical trifluoromethylthiolation- boration of alkynes

图式20. SCF3自由基引发的烯烃双官能化反应 SCF3自由基引发的烯烃双官能化反应

Scheme 20. Difunctionalization of alkenes initiated by SCF3 radicals

图式21. 三氟甲基硫自由基介导的重排反应

Scheme 21. SCF3-radical mediated rearrangements

图式22. 三氟甲基硫自由基介导的重排反应机理

Scheme 22. Proposed reaction pathways of the SCF3-radical mediated rearrangements

参考文献 26

[1]	(a) Chu, L.; Qing, F.-L. Acc. Chem. Res. 2014, 47, 1513. doi: 10.1021/ar4003202
	(b) Ni, C.; Hu, J. Chem. Soc. Rev. 2016, 45, 5441. doi: 10.1039/C6CS00351F
	(c) Zhang, X.; Tang, P. Sci. China: Chem. 2019, 62, 525. doi: 10.1007/s11426-018-9402-x
	(d) Feng, Z.; Xiao, Y.-L.; Zhang, X. Acc. Chem. Res. 2018, 51, 2264. doi: 10.1021/acs.accounts.8b00230
	(e) Zhang, C.-P.; Chen, Q.-Y.; Guo, Y.; Xiao, J.-C.; Gu, Y.-C. Chem. Soc. Rev. 2012, 41, 4536. doi: 10.1039/c2cs15352a
[2]	(a) Dong, D.-Q.; Yang, H.; Shi, J.-L.; Si, W.-J.; Wang, Z.-L.; Xu, X.-M. Org. Chem. Front. 2020, 7, 2538. doi: 10.1039/D0QO00567C
	(b) Wang, Z.; Sun, Y.; Shen, L.-Y.; Yang, W.; Meng, F.; Li, P. Org. Chem. Front. 2022, 9, 853. doi: 10.1039/D1QO01512E
[3]	(a) Zhang, K.; Xu, X.; Qing, F. Chin. J. Org. Chem. 2015, 35, 556. (in Chinese) doi: 10.6023/cjoc201501017
	(张柯, 徐修华, 卿凤翎, 有机化学, 2015, 35, 556.) doi: 10.6023/cjoc201501017
	(b) Shao, X.; Xu, C.; Lu, L.; Shen, Q. Acc. Chem. Res. 2015, 48, 1227. doi: 10.1021/acs.accounts.5b00047
[4]	(a) Yang, W.-C.; Feng, J.-G.; Wu, L.; Zhang, Y.-Q. Adv. Synth. Catal. 2019, 361, 1700. doi: 10.1002/adsc.201801355
	(b) Si, Y.-F.; Lv, Q.-Y.; Yu, B. Adv. Synth. Catal. 2021, 363, 4640. doi: 10.1002/adsc.202100807
	(c) Lv, Y.; Cui, H.; Meng, N.; Yue, H.; Wei, W. Chin. Chem. Lett. 2022, 33, 97. doi: 10.1016/j.cclet.2021.06.068
[5]	Yin, F.; Wang, X.-S. Org. Lett. 2014, 16, 1128. doi: 10.1021/ol403739w
[6]	(a) Fuentes, N.; Kong, W.; Fernández-Sánchez, L.; Merino, E.; Nevado, C. J. Am. Chem. Soc. 2015, 137, 964. doi: 10.1021/ja5115858 pmid: 25561161
	(b) Li, M.; Sun, K. Chin. J. Org. Chem. 2022, 42, 2089. (in Chinese) doi: 10.6023/cjoc202203001 pmid: 25561161
	(李猛, 孙凯, 有机化学, 2022, 42, 2089.) doi: 10.6023/cjoc202203001 pmid: 25561161
[7]	(a) Honeker, R.; Garza-Sanchez, R. A.; Hopkinson, M. N.; Glorius, F. Chem.-Eur. J. 2016, 22, 4395. doi: 10.1002/chem.201600190 pmid: 26880666
	(b) Dagousset, G.; Simon, C.; Anselmi, E.; Tuccio, B.; Billard, T.; Magnier, E. Chem.-Eur. J. 2017, 23, 4282. doi: 10.1002/chem.201700734 pmid: 26880666
[8]	Chen, M.-T.; Tang, X.-Y.; Shi, M. Org. Chem. Front. 2017, 4, 86. doi: 10.1039/C6QO00536E
[9]	Liu, B.; Wang, Z.; Sun, K.; Tang, S.; Wang, X. Chin. J. Org. Chem. 2022, 42, 1387. (in Chinese) doi: 10.6023/cjoc202203053
	(刘冰, 王智传, 孙凯, 唐石, 王薪, 有机化学, 2022, 42, 1387.) doi: 10.6023/cjoc202203053
[10]	Guo, J.; Hao, Y.; Li, G.; Wang, Z.; Liu, Y.; Li, Y.; Wang, Q. Org. Biomol. Chem. 2020, 18, 1994. doi: 10.1039/D0OB00233J
[11]	Yang, W.; Yang, S.; Li, P.; Wang, L. Chem. Commun. 2015, 51, 7520. doi: 10.1039/C5CC00878F
[12]	Song, Y.-K.; Qian, P.-C.; Chen, F.; Deng, C.-L.; Zhang, X.-G. Tetrahedron 2016, 72, 7589. doi: 10.1016/j.tet.2016.10.013
[13]	Wang, L.; Wang, H.; Meng, W.; Xu, X.-H.; Huang, Y. Chin. Chem. Lett. 2021, 32, 389. doi: 10.1016/j.cclet.2020.02.040
[14]	Qiu, Y.-F.; Zhu, X.-Y.; Li, Y.-X.; He, Y.-T.; Yang, F.; Wang, J.; Hua, H.-L.; Zheng, L.; Wang, L.-C.; Liu, X.-Y.; Liang, Y.-M. Org. Lett. 2015, 17, 3694. doi: 10.1021/acs.orglett.5b01657
[15]	Zeng, Y.-F.; Tan, D.-H.; Chen, Y.; Lv, W.-X.; Liu, X.-G.; Li, Q.; Wang, H. Org. Chem. Front. 2015, 2, 1511. doi: 10.1039/C5QO00271K
[16]	(a) Yang, W.-C.; Zhang, M.-M.; Feng, J.-G. Adv. Synth. Catal. 2020, 362, 4446. doi: 10.1002/adsc.202000636
	(b) Jin, D.-P.; Gao, P.; Chen, D.-Q.; Chen, S.; Wang, J.; Liu, X.-Y.; Liang, Y.-M. Org. Lett. 2016, 18, 3486. doi: 10.1021/acs.orglett.6b01702
	(c) Zhang, M.; Shen, L.; Dong, S.; Li, B.; Meng, F.; Si, W.; Yang, W. Eur. J. Org. Chem. 2021, 2021, 4465. doi: 10.1002/ejoc.202100656
	(d) Shen, L.; Sun, Y.; Wang, Y.; Li, B.; Yang, W.; Dai, P. Tetrahedron 2022, 106-107, 132649. doi: 10.1016/j.tet.2022.132649
	(e) Feng, J.; Chen, W.; Liu, Q.; Chen, Z.; Yang, J.; Yang, W. Pest Manage. Sci. 2020, 76, 4192. doi: 10.1002/ps.5976
[17]	Bi, M.-X.; Liu, S.; Huang, Y.; Xu, X.-H.; Qing, F.-L. Beilstein J. Org. Chem. 2020, 16, 657. doi: 10.3762/bjoc.16.62
[18]	(a) Jiang, Y.; Xu, K.; Zeng, C. Chem. Rev. 2018, 118, 4485. doi: 10.1021/acs.chemrev.7b00271
	(b) Zhang, M.-M.; Sun, Y.; Wang, W.-W.; Chen, K.-K.; Yang, W.-C.; Wang, L. Org. Biomol. Chem. 2021, 19, 3844. doi: 10.1039/D1OB00079A
	(c) Jiao, K.-J.; Xing, Y.-K.; Yang, Q.-L.; Qiu, H.; Mei, T.-S. Acc. Chem. Res. 2020, 53, 300. doi: 10.1021/acs.accounts.9b00603
	(d) Xiong, P.; Xu, H.-C. Acc. Chem. Res. 2019, 52, 3339. doi: 10.1021/acs.accounts.9b00472
	(e) Yang, W.-C.; Zhang, M.-M.; Sun, Y.; Chen, C.-Y.; Wang, L. Org. Lett. 2021, 23, 6691. doi: 10.1021/acs.orglett.1c02260
	(g) Jiang, Y.-M.; Yu, Y.; Wu, S.-F.; Yan, H.; Yuan, Y.; Ye, K.-Y. Chem. Commun. 2021, 57, 11484.
[19]	(a) Wu, W.; Dai, W.; Ji, X.; Cao, S. Org. Lett. 2016, 18, 2918. doi: 10.1021/acs.orglett.6b01286
	(b) Zheng, C.; Huang, S.; Liu, Y.; Jiang, C.; Zhang, W.; Fang, G.; Hong, J. Org. Lett. 2020, 22, 4868. doi: 10.1021/acs.orglett.0c01714
[20]	(a) Guo, C.-H.; Chen, D.-Q.; Chen, S.; Liu, X.-Y. Adv. Synth. Catal. 2017, 359, 2901. doi: 10.1002/adsc.201700534
	(b) Li, H.; Liu, S.; Huang, Y.; Xu, X.-H.; Qing, F.-L. Chem. Commun. 2017, 53, 10136. doi: 10.1039/C7CC06232J
[21]	(a) Pan, S.; Li, H.; Huang, Y.; Xu, X.-H.; Qing, F.-L. Org. Lett. 2017, 19, 3247. doi: 10.1021/acs.orglett.7b01366
	(b) Cheng, Z.-F.; Tao, T.-T.; Feng, Y.-S.; Tang, W.-K.; Xu, J.; Dai, J.-J.; Xu, H.-J. J. Org. Chem. 2018, 83, 499. doi: 10.1021/acs.joc.7b02232
	(c) Wang, J.-Y.; Ma, L.; Li, Y.; Wang, X. Chin. J. Org. Chem. 2019, 39, 232. (in Chinese)
	(王建勇, 马岚, 李彦, 王细胜, 有机化学, 2019, 39, 232.) doi: 10.6023/cjoc201807052
[22]	Ouyang, Y.; Xu, X.-H.; Qing, F.-L. Angew. Chem., Int. Ed. 2019, 58, 18508. doi: 10.1002/anie.201911323 pmid: 31612551
[23]	Zhang, Q.; Li, X.; Zhang, W.; Wang, Y.; Pan, Y. Org. Lett. 2021, 23, 5410. doi: 10.1021/acs.orglett.1c01737
[24]	(a) Zhang, X.-G.; He, Z.-X.; Guo, P.; Chen, Z.; Ye, K.-Y.; Org. Lett. 2022, 24, 22. doi: 10.1021/acs.orglett.1c03511
	(b) Li, D.; Yang, W. Tetrahedron Lett. 2019, 60, 1792. doi: 10.1016/j.tetlet.2019.06.005
	(c) Yang, W.; Li, B.; Zhang, M.; Wang, S.; Ji, Y.; Dong, S.; Feng, J.; Yuan, S. Chin. Chem. Lett. 2020, 31, 1313. doi: 10.1016/j.cclet.2019.10.022
	(d) Shi, Y.-F.; Lv, Q.-Y.; Yu, B. Adv. Synth. Catal. 2021, 363, 4640. doi: 10.1002/adsc.202100807
	(e) Wang, X.; Lei, J.; Guo, S.; Zhang, Y.; Ye, Y.; Tang, S.; Sun, K. Chem. Commun. 2022, 58, 1526. doi: 10.1039/D1CC06323E
[25]	(a) Pan, S.; Huang, Y.; Xu, X.-H.; Qing, F.-L. Org. Lett. 2017, 19, 4624. doi: 10.1021/acs.orglett.7b02249
	(b) Li, Y.; Koike, T.; Akita, M. Asian J. Org. Chem. 2017, 6, 445. doi: 10.1002/ajoc.201600562
	(c) Li, X.; Zhang, Q.; Zhang, W.; Ma, J.; Wang, Y.; Pan, Y. Beilstein J. Org. Chem. 2021, 17, 551. doi: 10.3762/bjoc.17.49
[26]	(a) Ji, M.; Yu, J.; Zhu, C. Chem. Commun. 2018, 54, 6812. doi: 10.1039/C8CC01189C
	(b) Wu, S.; Wu, X.; Wu, Z.; Zhu, C. Sci. China: Chem. 2019, 62, 1507. doi: 10.1007/s11426-019-9527-5
	(c) Liu, K.; Jin, Q.; Chen, S.; Liu, P. RSC Adv. 2017, 7, 1546. doi: 10.1039/C6RA25378D
	(d) Chen, D.; Ji, M.; Yao, Y.; Zhu, C. Acta Chim. Sinica 2018, 76, 951. (in Chinese) doi: 10.6023/A18080313
	(陈栋, 吉梅山, 姚英明, 朱晨, 化学学报, 2018, 76, 951.) doi: 10.6023/A18080313
	(e) Zhang, H.; Ji, M.; Wei, Y.; Chen, H.; Wu, X.; Zhu, C. Synlett 2021, 32, 401. doi: 10.1055/s-0040-1705968
	(f) Ji, M.; Wu, Z.; Yu, J.; Wan, X.; Zhu, C. Adv. Synth. Catal. 2017, 359, 1959. doi: 10.1002/adsc.201700218