银介导的自由基三氟甲硫化环化: 含CF3S苯并咪唑[2,1-a]异喹啉的合成

doi:10.6023/cjoc202203053

摘要/Abstract

开发了一种实用的银催化三氟甲硫化环化反应, 合成了各种结构多样的含CF₃S的苯并咪唑[2,1-a]异喹啉, 产率中等至良好. 机理研究表明, 催化反应通过CF₃S自由基引发的串联环化途径进行.

A practical Ag-catalyzed trifluoromethylthiolation cyclization reaction was developed. Various structurally diverse CF₃S-containing benzimidazo[2,1-a]isoquinolines were obtained for the first time in moderate to good yields. Mechanistic studies suggested that the catalytic reaction proceeds via a CF₃S-radical-triggered cascade cyclization pathway.

Key words: trifluoromethylthiolation, radical, cyclization, N-heterocycles

引用此文

刘冰, 王智传, 孙凯, 唐石, 王薪. 银介导的自由基三氟甲硫化环化: 含CF₃S苯并咪唑[2,1-a]异喹啉的合成[J]. 有机化学, 2022, 42(5): 1387-1395.

Bing Liu, Zhichuang Wang, Kai Sun, Shi Tang, Xin Wang. Silver-Mediated Radical Trifluoromethylthiolation Cyclization: Synthesis of CF₃S-Containing Benzimidazole[2,1-a]isoquinolines[J]. Chinese Journal of Organic Chemistry, 2022, 42(5): 1387-1395.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 6

参考文献 12

[1]	(b) Candeias, N. R.; Branco, L. C.; Gois, P. M. P.; Afonso, C. A. M.; Trindade, A. F. Chem. Rev. 2009, 109, 2703. doi: 10.1021/cr800462w pmid: 28051855
	(c) Shin, K.; Kim, H.; Chang, S. Acc. Chem. Res. 2015, 48, 1040. doi: 10.1021/acs.accounts.5b00020 pmid: 28051855
	(d) Jiao, J.; Kei, M.; Kenichiro, I. ACS Catal. 2016, 6, 610. doi: 10.1021/acscatal.5b02417 pmid: 28051855
	(e) Subramanian, P.; Rudolf, G. C.; Kaliappan, K. P. Chem. Asian J. 2016, 11, 168. doi: 10.1002/asia.201500361 pmid: 28051855
	(f) Yoonsu, P.; Youyoung, K.; Sukbok, C. Chem. Rev. 2017, 117, 9247. doi: 10.1021/acs.chemrev.6b00644 pmid: 28051855
[2]	McGrath, N. A.; Brichacek, M.; Njardarson, J. T. J. Chem. Educ. 2010, 87, 1348. doi: 10.1021/ed1003806
[3]	(a) Patil, N. T.; Yamamoto, Y. Chem. Rev. 2008, 108, 3395. doi: 10.1021/cr050041j
	(b) Lygin, A. V.; Meijere, A. D. Angew. Chem., Int. Ed. 2010, 49, 9094. doi: 10.1002/anie.201000723
	(c) Guo, X.-X.; Gu, D.-W.; Wu, Z.-X.; Zhang, W.-B. Chem. Rev. 2015, 115, 1622. doi: 10.1021/cr500410y
	(d) Alam, K.; Hong, S. W.; Oh, K. H.; Park, J. K. Angew. Chem.,Int. Ed. 2017, 56, 13387. doi: 10.1002/anie.201705514
	(e) Sun, K.; Si, Y.-F.; Chen, X.-L.; Lv, Q.-Y.; Peng, Y.-Y.; Qu, L.-B.; Yu, B. Asian J. Org. Chem. 2019, 8, 2042. doi: 10.1002/ajoc.201900570
	(f) Deady, L. W.; Rodemann, T. Aust. J. Chem. 2001, 54, 529. doi: 10.1071/CH01114
[4]	(a) Meng, G.; Niu, H.-Y.; Qu, G.-R.; Fossey, J. S.; Li, J.-P.; Guo, H.-M. Chem. Commun. 2012, 48, 9601. doi: 10.1039/c2cc34158a
	(b) Iaroshenko, V. O.; Ostrovskyi, D.; Miliutina, M.; Maalik, A.; Villinger, A.; Tolmachev, A.; Volochnyuk, D. M.; Langer, P. Adv. Synth. Catal. 2012, 354, 2495. doi: 10.1002/adsc.201200221
	(c) Sun, X.; Hu, X.; Nie, S.-Z.; Yan, Y.-Y.; Zhang, X.-J.; Yan, M. Adv. Synth. Catal. 2013, 355, 2179. doi: 10.1002/adsc.201300455
	(d) Sun, X.; Lv, X.-H.; Ye, L.-M.; Hu, Y.; Chen, Y.-Y.; Zhang, X.-J.; Yan, M. Org. Biomol. Chem. 2015, 13, 7381. doi: 10.1039/C5OB00904A
	(e) Liu, Y.-G.; Chen, G.-Q.; Tse, C.-W.; Guan, X.-G.; Xu, Z.-J.; Huang, J.-S.; Che, C.-M. Chem. Asian J. 2015, 10, 100. doi: 10.1002/asia.201402580
[1]	(a) Ricci, A. Amino Group Chemistry: From Synthesis to The Life Sciences,Wiley-VCH, Weinheim, 2008. pmid: 28051855
[4]	(f) Nguyen, T. B.; Ermolenkoa, L. Chem. Commun. 2016, 52, 4914 doi: 10.1039/C6CC01436D
[5]	(a) Müller, K.; Faeh, C.; Diederich, F. Science 2007, 317, 1881. doi: 10.1126/science.1131943
	(b) Hird, M. Chem. Soc. Rev. 2007, 36, 2070. doi: 10.1039/b610738a
	(c) Purser, S.; Moore, P. R.; Swallow, S.; Gouverneur, S. V. Chem. Soc. Rev. 2008, 37, 320. doi: 10.1039/B610213C
	(d) Wang, J.; Sánchez-Roselló, M.; Aceña, J. L.; del Pozo, C.; Sorochinsky, A. E.; Fustero, S.; Soloshonok, V. A.; Liu, H. Chem. Rev. 2014, 114, 2432. doi: 10.1021/cr4002879
	(e) Wang, S.-W.; Yu, J.; Zhou, Q.-Y.; Chen, S.-Y.; Xu, Z.-H.; Tang, S. ACS Sustainable Chem. Eng. 2019, 7, 10154. doi: 10.1021/acssuschemeng.9b02178
[6]	(a) Leo, A.; Hansch, C.; Elkins, D. Chem. Rev. 1971, 71, 525. doi: 10.1021/cr60274a001
	(b) Yagupol’skii, L. M.; Il’chenko, A. Y.; Kondratenko, N. V. Russ. Chem. Rev. 1974, 43, 1. doi: 10.1070/RC1974v043n01ABEH001785
	(c) Hansch, C.; Leo, A.; Taft, R. W. Chem. Rev. 1991, 91, 165. doi: 10.1021/cr00002a004
	(d) Leroux, F. Jeschke, P.; Schlosser, M. Chem. Rev. 2005, 105, 827. doi: 10.1021/cr040075b
	(e) Manteau, B.; Pazenok, S.; Vors, J. P.; Leroux, F. R. J. Fluorine Chem. 2010, 131, 140. doi: 10.1016/j.jfluchem.2009.09.009
	(f) Zhang, K.; Xu, X.-H.; Qing, F.-L. 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
	(g) Lang, B.; Suleman, M.; Lu, P.; Wang, Y.-G. Chin. J. Org. Chem. 2020, 40, 3300. (in Chinese) doi: 10.6023/cjoc202005011
	(郎勃, Muhammad, Suleman, 吕萍, 王彦广, 有机化学, 2020, 40, 3300.) doi: 10.6023/cjoc202005011
[7]	(a) Parsons, P. J.; Penkett, C. S.; Shell, A. J. Chem. Rev. 1996, 96, 195. pmid: 23121090
	(b) Wille, U. Chem. Rev. 2013, 113, 813. doi: 10.1021/cr100359d pmid: 23121090
	(c) Chen, N.; Lei, J.; Wang, Z.-C.; Liu, Y.-J.; Sun, K.; Tang, S. Chin. J. Org. Chem. 2022, 42, 1061. (in Chinese) doi: 10.6023/cjoc202109033 pmid: 23121090
	(陈宁, 雷佳, 王智传, 刘颖杰, 孙凯, 唐石, 有机化学, 2022, 42, 1061.) doi: 10.6023/cjoc202109033 pmid: 23121090
	(d) Wang, X.; Zhang, Y.; Sun, K.; Meng, J.-P.; Zhang, B. Chin. J. Org. Chem. 2021, 41, 4588. (in Chinese) doi: 10.6023/cjoc202109046 pmid: 23121090
	(王薪, 张艳, 孙凯, 孟建萍, 张冰, 有机化学, 2021, 41, 4588.) doi: 10.6023/cjoc202109046 pmid: 23121090
[8]	Yin, F.; Wang, X.-S. Org. Lett. 2014, 16, 1128. doi: 10.1021/ol403739w
[9]	Zeng, F.-L.; Sun, K.; Chen, X.-L.; Yuan, X.-Y.; He, S.-Q.; Liu, Y.; Peng, Y.-Y.; Qu, L.-B.; Lv, Q.-Y.; Yu, B. Adv. Synth. Catal. 2019, 361, 5176. doi: 10.1002/adsc.201901016
[10]	Lin, S.-N.; Cui, J.-C.; Chen, Y.; Li, Y. J. Org. Chem. 2021, 86, 15768. doi: 10.1021/acs.joc.1c01832
[11]	(a) Sun, K.; Li, Y.-L.; Feng, R.-R.; Mu, S.-Q.; Wan, X.; Zhang, B. J. Org. Chem. 2020, 85, 1001. doi: 10.1021/acs.joc.9b02941
	(b) Sun, K.; Wang, X.; Li, C.; Wang, H.; Li, L. Org. Chem. Front. 2020, 7, 3100. doi: 10.1039/D0QO00849D
	(c) Sun, K.; Lei, J.; Liu, Y.; Liu, B.; Chen, N. Adv. Synth. Catal. 2020, 362, 3709. doi: 10.1002/adsc.202000876
	(d) Sun, K.; Li, G.-F.; Li, Y.-Y.; Yu, J.; Zhao, Q.; Zhang, Z.-G.; Zhang, G.-S. Adv. Synth. Catal. 2020, 362, 1947. doi: 10.1002/adsc.202000040
	(e) Wang, X.; Guo, S.; Zhang, Y.; Zhang, Z.; Zhang, G.; Ye, Y.; Sun, K. Adv. Synth. Catal. 2021, 363, 3290. doi: 10.1002/adsc.202100208
	(f) Lv, Y.-H.; Meng, J.-P.; Li, C.; Wang, X.; Ye, Y.; Sun, K. Adv. Synth. Catal. 2021, 363, 5235. doi: 10.1002/adsc.202101184
	(g) Zhao, F.; Guo, S.; Zhang, Y.; Sun, T.; Yang, B.; Ye, Y.; Sun, K. Org. Chem. Front. 2021, 8, 6859.
	(h) Zhang, Z.; Wang, S.-L.; Tan, P.-P.; Gu, X.-W.; Sun, W.-J.; Liu, C.; Chen, J.-C.; Li, J.-Z.; Sun, K. Org. Lett. 2022, 24, 2288. doi: 10.1021/acs.orglett.2c00387
[12]	(a) Hu, M.; Fan, J.-H.; Liu, Y.; Ouyang, X.-H.; Song, R.-J.; Li, J.-H. Angew. Chem., Int. Ed. 2015, 54, 9577. doi: 10.1002/anie.201504603
	(b) Hu, M.; Song, R.-J.; Li, J.-H. Angew. Chem.,Int. Ed. 2015, 54, 608.
	(c) Guo, S.; Zhang, X.; Tang, P. Angew. Chem., nt. Ed. 2015, 54, 4065.
	(d) Wu, H.; Xiao, Z.; Wu, J.; Guo, Y.; Xiao, J.-C.; Liu, C.; Chen, Q.-Y. Angew. Chem., nt. Ed. 2015, 54, 4070.
	(e) Wang, C.; Song, R.-J.; Li, J.-H. Org. Lett. 2019, 21, 2800. doi: 10.1021/acs.orglett.9b00771
	(f) Guo, Y.-H.; Xiang, Y.-F.; Wei, L.; Wan, J.-P. Org. Lett. 2018, 20, 3971. doi: 10.1021/acs.orglett.8b01536
	(g) Wang, L.-L.; Zhang, Y.-L.; Zhang, M.; Bao, P.-L.; Lv, X.-X.; Liu, H.-G.; Zhao, X.-H.; Li, J.-S.; Luo, Z.-D.; Wei, W. Tetrahedron Lett. 2019, 60, 1845. doi: 10.1016/j.tetlet.2019.06.017
	(h) Li, G.-Q.; Gan, Z.-Y.; Kong, K.-X.; Dou, X.-M.; Yang, D.-S. Adv. Synth. Catal. 2019, 361, 1808. doi: 10.1002/adsc.201900157
	(i) Zhang, T.-S.; Zhang, H.-P.; Fu, R.; Wang, J.-Y.; Hao, W.-J.; Tu, S.-J.; Jiang, B. Chem. Commun. 2019, 55, 13231. doi: 10.1039/C9CC07236E
	(j) Ji, L.; Deng, Q.-F.; Liu, P.; Sun, P.-P. Org. Biomol. Chem. 2019, 17, 7715. doi: 10.1039/C9OB01396B
	(k) Wan, J.-P.; Tu, Z.; Wang, Y.-Y. Chem.-Eur. J. 2019, 25, 6907. doi: 10.1002/chem.201901025
	(l) Tian, L.-H.; Guo, Y.-H.; Wei, L.; Wan, J.-P.; Sheng, S.-R. Asian J. Org. Chem. 2019, 8, 1484. doi: 10.1002/ajoc.201900373
	(m) Liu, Y.-Y.; Xiong, J.; Wei, L.; Wan, J.-P. Adv. Synth. Catal. 2020, 362, 877. doi: 10.1002/adsc.201901234
	(n) Yang, W.-C.; Zhang, M.-M.; Chen, W.; Yang, X.-H.; Feng, J.-G. Chin. J. Org. Chem. 2020, 40, 4060. (in Chinese) doi: 10.6023/cjoc202005039
	(杨文超, 张明明, 陈旺, 杨小虎, 冯建国, 有机化学, 2020, 40, 4060.) doi: 10.6023/cjoc202005039

Entry	Oxidant/equiv.	Additive/equiv.	V(solvent)/ mL	Yield/%
1	K₂S₂O₈ (2.0)	None	DMSO	52
2	K₂S₂O₈ (2.0)	None	MeCN	17
3	K₂S₂O₈ (2.0)	None	DCE	0
4	K₂S₂O₈ (2.0)	None	THF	21
5	K₂S₂O₈ (1.0)	None	DMSO	50
6	PIDA (1.0)	None	DMSO	38
7	Selectfluor (1.0)	None	DMSO	0
8	TBHP (1.0)	None	DMSO	Trace
9	(NH₄)₂S₂O₈(1.0)	None	DMSO	51
10	K₂S₂O₈ (1.0)	KH₂PO₄ (1.5)	DMSO	62
11	K₂S₂O₈ (1.0)	HMPA (1.5)	DMSO	Trace
12	K₂S₂O₈ (1.0)	Li₂CO₃(1.5)	DMSO	35
13	K₂S₂O₈ (1.0)	NaHCO₃(1.5)	DMSO	48
14	K₂S₂O₈ (1.0)	KHCO₃(1.5)	DMSO	47
15	K₂S₂O₈ (1.0)	Na₂CO₃(1.5)	DMSO	50
16	K₂S₂O₈ (1.0)	DBU (1.5)	DMSO	53
17	K₂S₂O₈ (1.0)	KH₂PO₄·3H₂O (1.5)	DMSO	65
18	K₂S₂O₈ (1.0)	KH₂PO₄·3H₂O (1.0)	DMSO	83
19	K₂S₂O₈ (1.0)	KH₂PO₄·3H₂O (0.5)	DMSO	64
20	K₂S₂O₈ (1.0)	KH₂PO₄·3H₂O (1.0)	DMSO	56^c
21	K₂S₂O₈ (1.0)	KH₂PO₄·3H₂O (1.0)	DMSO	70^d

Entry	Oxidant/equiv.	Additive/equiv.	V(solvent)/ mL	Yield/%
1	K₂S₂O₈ (2.0)	None	DMSO	52
2	K₂S₂O₈ (2.0)	None	MeCN	17
3	K₂S₂O₈ (2.0)	None	DCE	0
4	K₂S₂O₈ (2.0)	None	THF	21
5	K₂S₂O₈ (1.0)	None	DMSO	50
6	PIDA (1.0)	None	DMSO	38
7	Selectfluor (1.0)	None	DMSO	0
8	TBHP (1.0)	None	DMSO	Trace
9	(NH₄)₂S₂O₈(1.0)	None	DMSO	51
10	K₂S₂O₈ (1.0)	KH₂PO₄ (1.5)	DMSO	62
11	K₂S₂O₈ (1.0)	HMPA (1.5)	DMSO	Trace
12	K₂S₂O₈ (1.0)	Li₂CO₃(1.5)	DMSO	35
13	K₂S₂O₈ (1.0)	NaHCO₃(1.5)	DMSO	48
14	K₂S₂O₈ (1.0)	KHCO₃(1.5)	DMSO	47
15	K₂S₂O₈ (1.0)	Na₂CO₃(1.5)	DMSO	50
16	K₂S₂O₈ (1.0)	DBU (1.5)	DMSO	53
17	K₂S₂O₈ (1.0)	KH₂PO₄·3H₂O (1.5)	DMSO	65
18	K₂S₂O₈ (1.0)	KH₂PO₄·3H₂O (1.0)	DMSO	83
19	K₂S₂O₈ (1.0)	KH₂PO₄·3H₂O (0.5)	DMSO	64
20	K₂S₂O₈ (1.0)	KH₂PO₄·3H₂O (1.0)	DMSO	56^c
21	K₂S₂O₈ (1.0)	KH₂PO₄·3H₂O (1.0)	DMSO	70^d

[1]	夏登鹏, 罗锦昀, 何林, 蔡志华, 杜广芬. 氮杂环卡宾催化的五氟苯基硫醚的合成[J]. 有机化学, 2024, 44(2): 622-630.
[2]	杨爽, 房新强. 氮杂环卡宾催化实现的动力学拆分近期研究进展[J]. 有机化学, 2024, 44(2): 448-480.
[3]	刘杰, 韩峰, 李双艳, 陈天煜, 陈建辉, 徐清. 无过渡金属参与甲基杂环化合物与醇的选择性有氧烯基化反应[J]. 有机化学, 2024, 44(2): 573-583.
[4]	高宝昌, 石雨, 田媛, 张治国, 张婧如, 孙宇峰, 毛国梁, 戴凌燕. 4-甲基-2-氧代-6-芳氨基-二氢-吡喃-3-腈衍生物的合成[J]. 有机化学, 2024, 44(2): 644-649.
[5]	童红恩, 郭宏宇, 周荣. 可见光促进惰性碳-氢键对羰基的加成反应进展[J]. 有机化学, 2024, 44(1): 54-69.
[6]	朱彦硕, 王红言, 舒朋华, 张克娜, 王琪琳. 烷氧自由基引发1,5-氢原子转移实现C(sp³)—H键官能团化的研究进展[J]. 有机化学, 2024, 44(1): 1-17.
[7]	金玉坤, 任保轶, 梁福顺. 可见光介导的三氟甲基的选择性C－F键断裂及其在偕二氟类化合物合成中的应用[J]. 有机化学, 2024, 44(1): 85-110.
[8]	贝文峰, 潘健, 冉冬梅, 刘伊琳, 杨震, 冯若昆. 基于钴催化吲哚酰胺与二炔和单炔的[4+2]环化反应合成γ-咔啉酮[J]. 有机化学, 2023, 43(9): 3226-3238.
[9]	徐伟, 翟宏斌, 程斌, 汪太民. 可见光诱导的钯催化Heck反应[J]. 有机化学, 2023, 43(9): 3035-3054.
[10]	张建涛, 张聪, 莫诺琳, 罗佳婷, 陈莲芬, 刘卫兵. 氯仿参与的烯烃自由基加成反应的研究进展[J]. 有机化学, 2023, 43(9): 3098-3106.
[11]	陈祖良, 魏颖静, 张俊良. 供体-受体氮杂环丙烷碳-碳键断裂的环加成反应研究进展[J]. 有机化学, 2023, 43(9): 3078-3088.
[12]	蔡远林, 吕亚, 聂桂花, 金智超, 池永贵. 氮杂环卡宾催化合成氰基化合物的研究进展[J]. 有机化学, 2023, 43(9): 3135-3145.
[13]	樊思捷, 董武恒, 梁彩云, 王贵超, 袁瑶, 尹作栋, 张兆国. 可见光诱导的自由基环化反应构建4-芳基-1,2-二氢萘类化合物[J]. 有机化学, 2023, 43(9): 3277-3286.
[14]	唐菁, 罗文坤, 周俊. 氮杂螺[4.5]三烯酮衍生物的合成研究进展[J]. 有机化学, 2023, 43(9): 3006-3034.
[15]	赵瑜, 张凯, 白育斌, 张琰图, 史时辉. 无金属条件下可见光催化与溴盐协同促进烯烃的氢硅化反应研究[J]. 有机化学, 2023, 43(8): 2837-2847.

银介导的自由基三氟甲硫化环化: 含CF₃S苯并咪唑[2,1-a]异喹啉的合成

Silver-Mediated Radical Trifluoromethylthiolation Cyclization: Synthesis of CF₃S-Containing Benzimidazole[2,1-a]isoquinolines

RichHTML

PDF

补充材料

可视化

摘要/Abstract

引用此文

分享此文

图/表 6

参考文献 12

相关文章 15

编辑推荐

相关统计

本文评价