烯胺调控下和对甲苯磺酰叠氮在纯水介质中的无金属环化反应合成1,2,3-三氮唑

doi:10.6023/cjoc202104053

摘要/Abstract

通过使用简单的Et₃N催化容易获得的β-取代NH-烯胺酯和对甲苯磺酰叠氮的反应, 高效实现了全取代的1,2,3-三氮唑的合成. 在该方法中, 水用作反应的唯一介质, 以高底物适用性和中等至优秀的产率合成了1,2,3-三氮唑产物. 对照实验表明, 使用稳定的NH-烯胺作为底物, 可能是通过NH基团与水之间的氢键作用实现水介导反应的关键因素. 研究还发现, 在相同条件下经由相应的N-烷基烯胺酯和对甲苯磺酰叠氮的反应, 选择性地生成N-烷基磺酰胺.

关键词: 烯胺, 环化反应, 无金属, 纯水介质, 1,2,3-三氮唑

The synthesis of full substituted 1,2,3-triazoles has been accomplished with high efficiency through the reactions of readily availableβ-substituted NH-enaminoesters and tosyl azide with Et₃N catalysis. In this method, water was used as the sole medium for the reactions which provide 1,2,3-triazole products with broad scope and moderate to excellent yield. Control experiments disclose that the employment of stable NH-enamines as substrates is the key factor enabling the water mediated synthesis probably via the hydrogen bonding effect between NH group and water. In addition, the novel and selective production ofN-alkyl sulfonamides via the reactions of correspondingN-alkyl enaminoesters and tosyl azide has been observed under identical conditions.

Key words: enamine, annulation, metal-free, pure water medium, 1,2,3-triazole

引用此文

郑茜茜, 刘云云, 万结平. 烯胺调控下和对甲苯磺酰叠氮在纯水介质中的无金属环化反应合成1,2,3-三氮唑[J]. 有机化学, 2021, 41(7): 2700-2706.

Xixi Zheng, Yunyun Liu, Jie-Ping Wan. Metal-Free Synthesis of 1,2,3-Triazoles in Pure Water via the Enamine Modified Annulation Reactions with Tosyl Azide[J]. Chinese Journal of Organic Chemistry, 2021, 41(7): 2700-2706.

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

分享此文

图/表 2

参考文献 19

[1]	(a) Lipshutz,B. H.; Ghorai, S.; Cortes-Clerget, M. Chem.-Eur. J. 2018, 24,6672. doi: 10.1002/chem.v24.26
	(b) Gawande,M. B.; Bonifácio,V. D.B.; Luque, R.; Branco,P. S.; Varma,R. S. Chem. Soc. Rev. 2013, 42,5522. doi: 10.1039/c3cs60025d
	(c) Anastas, P.; Eghbali, N. Chem. Soc. Rev. 2010, 39,301. doi: 10.1039/B918763B
[2]	(a) Butler,R. N.; Goyne,A. G. Chem. Rev. 2010, 110,6302. doi: 10.1021/cr100162c
	(b) Chanda, A.; Fokin,V. V. Chem. Rev. 2009, 109,725. doi: 10.1021/cr800448q
	(c) Sun, K.; Lv,Q. -Y.; Chen,X. -L.; Qu,L. -B.; Yu, B. Green Chem. 2021, 23,232. doi: 10.1039/D0GC03447A
	(d) Chen, D.; Liu, J.; Zhang, X.; Jiang, H.; Li, J. Chin. J. Org. Chem. 2019, 39,3353 (in Chinese). doi: 10.6023/cjoc201907014
	( 陈丹, 刘剑沉, 张馨元, 蒋合众, 李加洪, 有机化学. 2019, 39,3353.)
[3]	(a) Li, Y.; Huang, Y.; Gui, Y.; Sun, J.; Li, J.; Zha, Z.; Wang, Z. Org. Lett. 2017, 19,6416. doi: 10.1021/acs.orglett.7b03299
	(b) Zhang, F.; Tian, Y.; Li, G.; Qu, J. J. Org. Chem. 2015, 80,1107. doi: 10.1021/jo502636d
	(c) Álvarez, M.; Gava, R.; Rodríguez,M. R.; Rull,S. G.; Pérez,P. J. ACS Catal. 2017, 7,3707. doi: 10.1021/acscatal.6b03669
	(d) Zhang, N.; Yang, D.; Wei, W.; Yuan, L.; Nie, F.; Tian, L.; Wang, H. J. Org. Chem. 2015, 80,3258. doi: 10.1021/jo502642n
	(e) Tang, S.; Li, L.; Ren, X.; Li, J.; Yang, G.; Li, H.; Yuan, B. Green Chem. 2019, 21,2899. doi: 10.1039/C8GC03815E
[4]	(a) Peng, S.; Song,Y. -X.; He,J. -Y.; Tang,S. -S.; Tan,J. -X.; Cao, Z.; Lin,Y. -W.; He,W. -M. Chin. Chem. Lett. 2019, 30,2287. doi: 10.1016/j.cclet.2019.08.002
	(b) Wu, Y.; Lin,Y. -W.; He,W. -M. Chin. Chem. Lett. 2020, 31,2999. doi: 10.1016/j.cclet.2020.09.005
	(c) Shukla, P.; Asati, A.; Bhardiya,S. R.; Singh, M.; Rai,V. K.; Rai, A. J. Org. Chem. 2020, 85,15552. doi: 10.1021/acs.joc.0c02219
[5]	(a) Tang, L.; Yang, Y.; Wen, L.; Yang, X.; Wang, Z. Green Chem. 2016, 18,1224. doi: 10.1039/C5GC02755A
	(b) Lin, Y.; Lu, G.; Wang, G.; Yi, W. J. Org. Chem. 2017, 82,382. doi: 10.1021/acs.joc.6b02459
[6]	(a) Chen, L.; Huang, R.; Li, K.; Yun,X. -H.; Yang,C. -L.; Yan,S. -J. Green Chem. 2020, 22,6943. doi: 10.1039/D0GC02460K
	(b) Husain,A. A.; Bisht, K. J. Org. Chem. 2020, 85,9928. doi: 10.1021/acs.joc.0c01150
	(c) Köhling, S.; Exner,M. P.; Nojoumi, S.; Schiller, J.; Budisa, N.; Rademann, J. Angew. Chem. Int. Ed. 2016, 55,15510. doi: 10.1002/anie.201607228
	(d) Yang, J.; Mei, F.; Fu, S.; Gu, Y. Green Chem. 2018, 20,1367. doi: 10.1039/C7GC03644B
	(e) Reddy,G. T.; Kumar, G.; Reddy,N. C.G. Adv. Synth. Catal. 2018, 360,995. doi: 10.1002/adsc.v360.5
	(f) Yang, L.; Wu, Y.; Yang, Y.; Wen, C.; Wan,J. -P. Beilstein J. Org. Chem. 2018, 14,2348. doi: 10.3762/bjoc.14.210
	(g) Chen, X.; Xia, F.; Zhao, Y.; Ma, J.; Zhang, D.; Yang, L. Sun, P. Chin. J. Chem. 2020, 38,1239. doi: 10.1002/cjoc.v38.11
	(h) Sun, G.; He, Y.; Tian, C.; Borzov, M.; Hu, Q.; Nie, W. Acta Chem. Sinica 2019, 77,166 (in Chinese).
	( 孙国峰, 何云清, 田冲, Borzov Maxim, 胡启山, 聂万丽, 化学学报, 2019, 77,166.)
[7]	(a) Meldal, M.; Tomøe,C. W. Chem. Rev. 2008, 108,2952. doi: 10.1021/cr0783479
	(b) Thirumurugan, P.; Matosiuk, D.; Jozwiak, K. Chem. Rev. 2013, 113,4905. doi: 10.1021/cr200409f
	(c) Jiang, Y.; Sun, R.; Tang,X. -Y.; Shi, M. Chem.-Eur. J. 2016, 22,17910. doi: 10.1002/chem.201601703
[8]	For selected reviews, see: (a) Opsomer, T.; Dehaen,, W. Chem. Commun. 2021, 57,1568. doi: 10.1039/D0CC06654K
	(b) Ramasastry,S. S.V. Angew. Chem. Int. Ed. 2014, 53,14310. doi: 10.1002/anie.201409410
	(c) Lima,C. G.S.; Ali, A.; Berkel,S. S.; Westermann, B.; Paixão,M. W. Chem. Commun. 2015, 51,10784. doi: 10.1039/C5CC04114G
[9]	(a) Ramachary,D. B.; Shashank,A. B.; Karthik, S. Angew. Chem. Int. Ed. 2014, 53,10420. doi: 10.1002/anie.201406721
	(b) Thomas, J.; John, J.; Parekh, N.; Dehaen, W. Angew. Chem. Int. Ed. 2014, 53,10155. doi: 10.1002/anie.201403453
	(c) Zhang, D.; Fan, Y.; Yan, Z.; Nie, Y.; Xiong, X.; Gao, L. Green Chem. 2019, 21,4211. doi: 10.1039/C9GC01129C
	(d) Reddy,G. S.; Reddy,L. M.; Kumar,A. S.; Ramachary,D. B. J. Org. Chem. 2020, 85,15488. doi: 10.1021/acs.joc.0c02247
[10]	(a) Belkheira, M.; Abed,D. E.; Pons,J. -M.; Bressy, C. Chem.-Eur. J. 2011, 17,12917. doi: 10.1002/chem.v17.46
	(b) Ramachary,D. B.; Krishna,P. M.; Gujral, J.; Reddy,G. S. Chem.-Eur. J. 2015, 21,16775. doi: 10.1002/chem.v21.47
	(c) Guo, N.; Liu, X.; Xu, H.; Zhou, X.; Zhao, H. Org. Biomol. Chem. 2019, 17,6148. doi: 10.1039/C9OB01156K
	(d) Danence,L. J.T.; Gao, Y.; Li, M.; Huang, Y.; Wang, J. Chem.-Eur. J. 2011, 17,3584. doi: 10.1002/chem.v17.13
	(e) Nelsona, R.; Kesternicha, V.; Pérez-Fehrmanna, M.; Jaldina, S.; Marcourtb, L.; Christen, P. J. Chem. Res. 2016, 40,453. doi: 10.3184/174751916X14656662266973
[11]	(a) Li, W.; Wang, J. Angew. Chem. Int. Ed. 2014, 53,14186. doi: 10.1002/anie.v53.51
	(b) Ramachary,D. B.; Ramakumar, K.; Narayana,V. V. Chem.-Eur. J. 2008, 14,9143. doi: 10.1002/chem.v14:30
	(c) Das, J.; Dey, S.; Pathak, T. J. Org. Chem. 2019, 84,15437. doi: 10.1021/acs.joc.9b02443
[12]	(a) Agard,N. J.; Prescher,J. A.; Bertozzi,C. R. J. Am. Chem. Soc. 2004, 126,15046. doi: 10.1021/ja044996f
	(b) Kwok,S. W.; Fotsing,J. R.; Fraser,R. J.; Rodionov,V. O.; Fokin,V. V. Org. Lett. 2010, 12,4217. doi: 10.1021/ol101568d
[13]	(a) Cheng, G.; Zeng, X.; Shen, J.; Wang, X.; Cui, X. Angew. Chem. Int. Ed. 2013, 52,13265. doi: 10.1002/anie.201307499
	(b) Wan,J. -P.; Cao, S.; Liu, Y. Org. Lett. 2016, 18,6034. doi: 10.1021/acs.orglett.6b02975
	(c) Deng, L.; Cao, X.; Liu, Y.; Wan,J. -P. J. Org. Chem. 2019, 84,14179. doi: 10.1021/acs.joc.9b01817
	(d) De Nino, A.; Algieri, V.; Talllarida, M.A.; Constanzo, P.; Pedron, M.; Tejero, T.; Merino, P.; Maiuolo, L. Eur. J. Org. Chem. 2019, 33,5725.
	(e) Huang, W.; Zhu, C.; Li, M.; Yu, Y.; Wu, W.; Tu, Z.; Jiang, H. Adv. Synth. Catal. 2018, 360,3117. doi: 10.1002/adsc.201800487
	(f) Thomas, J.; Goyvaerts, V.; Liekens, S.; Dehaen, W. Chem.-Eur. J. 2016, 22,9966.
	(g) Cao, S.; Liu, Y.; Hu, C.; Wen, C.; Wan,J. -P. ChemCatChem 2018, 10,5007. doi: 10.1002/cctc.v10.21
[14]	(a) Shu,W. -M.; Zhang,X. -F.; Zhang,X. -X.; Li, M.; Wang,A. -J.; Wu,A. -X. J. Org. Chem. 2019, 84,14919. doi: 10.1021/acs.joc.9b02250
	(b) Berkel,S. S.; Brauch, S.; Gabriel, L.; Henze, M.; Stark, S.; Vasilev, D.; Wessjohann,L. A.; Abbas, M.; Westermann, B. Angew. Chem. Int. Ed. 2012, 51,5343. doi: 10.1002/anie.201108850
[15]	For reviews and selected examples, see: (a) Wan,J. -P.; Hu, D.; Liu, Y.; Sheng,, S. ChemCatChem 2015, 7,901. doi: 10.1002/cctc.201500001
	(b) Chen, Z.; Gao, G.; Song, J.; Ren, H. Chin. J. Chem. 2017, 35,1797. doi: 10.1002/cjoc.v35.12
	(c) Shang,Z. -H.; Zhang,Z. -X.; Weng,W. -Z.; Wang,Y. -F.; Cheng,T. -W.; Zhang,Q. -Y.; Song,L. -Q.; Shao,T. -Q.; Liu,K. -X.; Zhu,Y. -P. Adv. Synth. Catal. 2020, 363,490. doi: 10.1002/adsc.v363.2
	(d) Wan,J. -P.; Cao, S.; Liu, Y. J. Org. Chem. 2015, 80,9028. doi: 10.1021/acs.joc.5b01121
	(e) Panda, S.; Maity, P.; Manna, D. Org. Lett. 2017, 19,1534. doi: 10.1021/acs.orglett.7b00313
	(f) Cai,Z. -J.; Lu,X. -M.; Zi, Y.; Yang, C.; Shen,L. -J.; Li, J.; Wang,S. -Y.; Ji,S. -J. Org. Lett. 2014, 16,5108. doi: 10.1021/ol502431b
	(g) Wu, P.; He, Y.; Wang, H.; Zhou,Y. -G.; Yu, Z. Org. Lett. 2020, 22,310. doi: 10.1021/acs.orglett.9b04335
	(h) Chen, Z.; Yan, Q.; Liu, Z.; Zhang, Y. Chem.-Eur. J. 2014, 20,17635. doi: 10.1002/chem.201405057
[16]	(a) Guo, Y.; Wang, G.; Wei, L.; Wan,J. -P. J. Org. Chem. 2019, 84,2984. doi: 10.1021/acs.joc.8b02897
	(b) Zheng, X.; Wan,J. -P. Adv. Synth. Catal. 2019, 361,5690. doi: 10.1002/adsc.v361.24
	(c) Gan, L.; Wei, L.; Wan,J. -P. ChemistrySelect 2020, 5,7822. doi: 10.1002/slct.v5.26
	(d) Fu, L.; Cao, X.; Wan,J. -P. Chin. J. Chem. 2020, 38,254. doi: 10.1002/cjoc.v38.3
[17]	For a few recent examples, see (a) Gan, L.; Yu, Y.; Liu, L.; Wan,J. -P. J. Org. Chem. 2021, 86,1231. doi: 10.1021/acs.joc.0c02431
	(b) Fu, L.; Xu, Z.; Wan,J. -P.; Liu, Y. Org. Lett. 2020, 24,9518.
	(c) Hu, D.; Yang, L.; Wan,J. -P. Green Chem. 2020, 22,6773. doi: 10.1039/D0GC02806A
	(d) Klintworth, R.; de Koning,C. B.; Opatz, T.; Michael,J. P. J. Org. Chem. 2019, 84,11025. doi: 10.1021/acs.joc.9b01604
	(e) Chen, J.; Guo, P.; Zhang, J.; Rong, J.; Sun, W.; Jiang, Y.; Loh,T. -P. Angew. Chem. Int. Ed. 2019, 58,12674. doi: 10.1002/anie.v58.36
	(f) Gao, Y.; Liu, Y.; Wan,J. -P. J. Org. Chem. 2019, 84,2243. doi: 10.1021/acs.joc.8b02981
	(g) Shang, Z.; Chen, Q.; Xing, L.; Zhang, Y.; Wait, L.; Du, Y. Adv. Synth. Catal. 2019, 361,4926. doi: 10.1002/adsc.v361.21
	(h) Zhou, P.; Hu, B.; Li, L.; Rao, K.; Yang, J.; Yu, F. J. Org. Chem. 2017, 82,13268. doi: 10.1021/acs.joc.7b02391
	(i) Gu, F.; Yao, W. Chin. J. Org. Chem. 2020, 40,4384 (in Chinese). doi: 10.6023/cjoc202000091
	( 谷枫, 姚伟军, 有机化学, 2020, 40,4384.)
	(j) Wang, G.; Guo, Y.; Wan,J. -P. Chin. J. Org. Chem. 2020, 40,645 (in Chinese). doi: 10.6023/cjoc201912018
	( 王国栋, 郭艳辉, 万结平, 有机化学, 2020, 40,645.)
	(k) Yu, Q.; Liu, Y.; Wan,J. -P. Chin. Chem. Lett. 2021,DOI: 10.1016/j.cclet.2021.04.037 doi: 10.1016/j.cclet.2021.04.037
[18]	(a) Nitin,A. R.; Varun K.; Vipin,A. N. Monatsh. Chem. 2010, 141,1329. doi: 10.1007/s00706-010-0399-9
	(b) Nishiwaki, N.; Nishimoto, T.; Tamura, M.; Ariga, M. Synlett 2006,1437.
[19]	Tang, X.; Huang, L.; Qi, C.; Wu, X.; Wu, W.; Jiang, H. Chem. Commun. 2013, 49,6102. doi: 10.1039/c3cc41249k