银催化下三氟甲基取代的2-咪唑啉化合物的合成

doi:10.6023/cjoc202111009

摘要/Abstract

探索了银盐催化下, 三氟甲基酰腙与异氰基乙酸乙酯的[3+2]环加成反应, 合成了一系列三氟甲基取代的2-咪唑啉化合物. 该方法具有反应速度快、产率高和立体选择性好等特点, 为合成三氟甲基取代的2-咪唑啉类化合物提供了一种快速有效的新方法．

关键词: 三氟甲基酰腙, 异氰基乙酸乙酯, [3+2]环加成, 2-咪唑啉

The silver salt catalyzed [3+2] cycloaddition reaction of trifluoromethylated N-acylhydrazones and ethyl isocyanoacetate was investigated. The reaction proceeds quickly to produce a series of trifluoromethylated 2-imidazoline compounds in high yields with excellent stereoselectivity, which provides a novel and efficient method for the synthesis of trifluoromethylated 2-imidazoline compounds.

Key words: trifluoromethylated N-acylhydrazone, ethyl isocyanoacetate, [3+2] cycloaddition, 2-imidazoline

引用此文

杨明, 黄丹凤, 王克虎, 韩侗育, 赵鹏飞, 王凤, 王君姣, 苏瀛鹏, 胡雨来. 银催化下三氟甲基取代的2-咪唑啉化合物的合成[J]. 有机化学, 2022, 42(5): 1509-1519.

Ming Yang, Danfeng Huang, Kehu Wang, Tongyu Han, Pengfei Zhao, Feng Wang, Junjiao Wang, Yingpeng Su, Yulai Hu. Silver-Catalyzed Synthesis of CF₃-Substituted 2-Imidazolines[J]. Chinese Journal of Organic Chemistry, 2022, 42(5): 1509-1519.

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

分享此文

图/表 6

参考文献 24

[1]	(a) Liu, H.; Du, D.-M. Adv. Synth. Catal. 2009, 351, 489. doi: 10.1002/adsc.200800797
	(b) Mehedi, M. S. A.; Tepe, J. J. Adv. Synth. Catal. 2020, 362, 4189. doi: 10.1002/adsc.202000709
[2]	(a) Murai, K.; Morishita, M.; Nakatani, R.; Kubo, O.; Fujioka, H.; Kita, Y. J. Org. Chem. 2007, 72, 8947. doi: 10.1021/jo701668s
	(b) Namba, K.; Takeuchi, K.; Kaihara, Y.; Oda, M.; Nakayama, A.; Nakayama, A.; Yoshida, M.; Tanino, K. Nat. Commun. 2015, 6, 8731. doi: 10.1038/ncomms9731
	(c) Liu, H. B.; Lauro, G.; O'Connor, R. D.; Lohith, K.; Kelly, M.; Colin, P.; Bifulco, G.; Bewley, C. A. J. Nat. Prod. 2017, 80, 2556. doi: 10.1021/acs.jnatprod.7b00452
	(d) Ohashi, E.; Karanjit, S.; Nakayama, A.; Takeuchi, K.; Emam, S. E.; Ando, H.; Ishida, T.; Namba, K. Chem. Sci. 2021, 12, 12201. doi: 10.1039/D1SC03260G
[3]	(a) Merriman, G. H.; Ma, L.; Shum, P.; McGarry, D.; Volz, F.; Sabol, J. S.; Gross, A.; Zhao, Z.; Rampe, D.; Wang, L.; Wirtz- Brugger, F.; Harris, B. A.; Macdonald, D. Bioorg. Med. Chem. Lett. 2005, 15, 435. pmid: 15603968
	(b) Vassilev, L. T. Trends Mol. Med. 2007, 13, 23. doi: 10.1016/j.molmed.2006.11.002 pmid: 15603968
	(c) Patel, S.; Player, M. R. Expert Opin. Invest. Drugs 2008, 17, 1865. doi: 10.1517/13543780802493366 pmid: 15603968
	(d) Naguy, A. Pharmacology 2016, 98, 87. doi: 10.1159/000446441 pmid: 15603968
	(e) Kahlon, D. K.; Lansdell, T. A.; Fisk, J. S.; Hupp, C. D.; Friebe, T. L.; Hovde, S.; Jones, A. D.; Dyer, R. D.; Henry, R. W.; Tepe, J. J. J. Med. Chem. 2009, 52, 1302. doi: 10.1021/jm8013162 pmid: 15603968
	(f) Sato, N.; Ando, M.; Ishikawa, S.; Jitsuoka, M.; Nagai, K.; Takahashi, H.; Sakuraba, A.; Tsuge, H.; Kitazawa, H.; Iwaasa, H.; Mashiko, S.; Gomori, A.; Moriya, R.; Fujino, N.; Ohe, T.; Ishihara, A. J. Med. Chem. 2009, 52, 3385. doi: 10.1021/jm900110t pmid: 15603968
	(g) Li, H.-Y.; Drummond, S.; DeLucca, I.; Boswell, G. A. Tetrahedron 1996, 52, 11153. doi: 10.1016/0040-4020(96)00578-9 pmid: 15603968
[4]	Sztanke, K.; Pasternak, K.; Sidor-Wojtowicz, A.; Truchlinska, J.; Jozwiak, K. Bioorg. Med. Chem. 2006, 14, 3635.
[5]	Bon, R. S.; van Vliet, B.; Sprenkels, N. E.; Schmitz, R. F.; de Kanter, F. J.; Stevens, C. V.; Swart, M.; Bickelhaupt, F. M.; Groen, M. B.; Orru, R. V. J. Org. Chem. 2005, 70, 3542. doi: 10.1021/jo050132g
[6]	Caignard, D. H.; Renard, P. Bioorg. Med. Chem. 2006, 14, 7419. doi: 10.1016/j.bmc.2006.07.026
[7]	Njomen, E.; Tepe, J. J. Cell Chem. Biol. 2019, 26, 1283. doi: S2451-9456(19)30210-7 pmid: 31327703
[8]	Njomen, E.; Tepe, J. J. J. Med. Chem. 2019, 62, 6469. doi: 10.1021/acs.jmedchem.9b00101 pmid: 30839208
[9]	(a) Puntener, K.; Hellman, M. D.; Kuester, E.; Hegedus, L. S. J. Org. Chem. 2000, 65, 8301. pmid: 10990421
	(b) Jung, M. E.; Huang, A. Org. Lett. 2000, 2, 2659. pmid: 10990421
[10]	(a) Corey, E. J.; Grogan, M. J. Org. Lett. 1999, 1, 157. doi: 10.1021/ol990623l pmid: 10822552
	(b) Isobe, T.; Fukuda, K.; Araki, Y.; Ishikawa, T. Chem. Commun. 2001, 243. pmid: 10822552
[11]	(a) Dalko, P. I.; Langlois, Y. Chem. Commun. 1998, 331.
	(b) Dalko, P. I.; Langlois, Y. J. Org. Chem. 1998, 63, 8107. doi: 10.1021/jo980289r
[12]	(a) Menges, F.; Neuburger, M.; Pfaltz, A. Org. Lett. 2002, 4, 4713. doi: 10.1021/ol027253c
	(b) Liu, H.; Du, D.-M. Adv. Synth. Catal. 2010, 352, 1113. doi: 10.1002/adsc.201000111
	(c) Awata, A.; Arai, T. Angew. Chem., Int. Ed. 2014, 53, 10462. doi: 10.1002/anie.201405223
[13]	Zhou, B.; Zhang, J.; Li, X.; She, M.; Zhang, J.; Li, J.; Shi, Z. Chin. J. Org. Chem. 2013, 33, 423. (in Chinese) doi: 10.6023/cjoc201207046
	(周葆悦, 张金, 李向南, 厍梦尧, 张劲, 李剑利, 史真, 有机化学, 2013, 33, 423.) doi: 10.6023/cjoc201207046
[14]	(a) Zhou, X.; Lin, Y.; Dai, Y.; Sun, J.; Xia, L.; Tang, M. J. Org. Chem. 1999, 64, 1331. doi: 10.1021/jo980949s
	(b) Hayashi, M.; Iwanaga, M.; Shiomi, N.; Nakane, D.; Masuda, H.; Nakamura, S. Angew. Chem., Int. Ed. 2014, 53, 8441. doi: 10.1002/anie.201402320
	(c) Ortin, I.; Dixon, D. J. Angew. Chem., Int. Ed. 2014, 53, 3462. doi: 10.1002/anie.201309719
	(d) Shao, P. L.; Liao, J. Y.; Ho, Y. A.; Zhao, Y. Angew. Chem., Int. Ed. 2014, 53, 5435. doi: 10.1002/anie.201402788
	(e) De La Campa, R.; Gammack Yamagata, A. D.; Ortin, I.; Franchino, A.; Thompson, A. L.; Odell, B.; Dixon, D. J. Chem. Commun. 2016, 52, 10632. doi: 10.1039/C6CC04132A
	(f) Nakamura, S.; Yamaji, R.; Iwanaga, M. Chem. Commun. 2016, 52, 7462. doi: 10.1039/C6CC02911F
	(g) Trulli, L.; Sciubba, F.; Fioravanti, S. Tetrahedron 2018, 74, 572. doi: 10.1016/j.tet.2017.12.029
	(h) Zhao, M. X.; Bi, H. L.; Jiang, R. H.; Xu, X. W.; Shi, M. Org. Lett. 2014, 16, 4566. doi: 10.1021/ol502123z
[15]	(a) Qing, F. Chin. J. Org. Chem. 2012, 32, 815. (in Chinese) doi: 10.6023/cjoc1202021 pmid: 26756377
	(卿凤翎, 有机化学, 2012, 32, 815.) doi: 10.6023/cjoc1202021 pmid: 26756377
	(b) Zhou, Y.; Wang, J.; Gu, Z.; Wang, S.; Zhu, W.; Aceña, J. L.; Soloshonok, V. A.; Izawa, K.; Liu, H. Chem. Rev. 2016, 116, 422. doi: 10.1021/acs.chemrev.5b00392 pmid: 26756377
	(c) 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 pmid: 26756377
	(d) Purser, S.; Moore, P. R.; Swallow, S.; Gouverneur, V. Chem. Soc. Rev. 2008, 37, 320. doi: 10.1039/B610213C pmid: 26756377
[16]	(a) Weaver, G. Angew. Chem., Int. Ed. 2010, 49, 5605. doi: 10.1002/anie.201003132
	(b) Meyer, F. Chem. Commun. 2016, 52, 3077. doi: 10.1039/C5CC09414C
	(c) Petrov, V. A. Fluorinated Heterocyclic Compounds: Synthesis, Chemistry, and Applications, Wiley, Hoboken, New Jersey, 2009.
[17]	Yoshiki, M.; Ishibashi, R.; Yamada, Y.; Hanamoto, T. Org. Lett. 2014, 16, 5509. doi: 10.1021/ol502331a
[18]	Zhang, X.; Wang, X.; Gao, Y.; Xu, X. Chem. Commun. 2017, 53, 2427. doi: 10.1039/C6CC10124K
[19]	(a) Wang, K. H.; Shi, B.; Wang, Y.; Wang, J.; Huang, D.; Su, Y.; Hu, Y. Asian J. Org. Chem. 2019, 8, 716. doi: 10.1002/ajoc.201800693
	(b) Hu, Y.; Huang, D.; Wang, K.; Zhao, F.; Zhao, Z.; Xu, W.; Hu, Y. Chin. J. Org. Chem. 2020, 40, 1689. (in Chinese) doi: 10.6023/cjoc201912006
	(虎永琴, 黄丹凤, 王克虎, 赵芳霞, 赵转霞, 徐炜刚, 胡雨来, 有机化学, 2020, 40, 1689.) doi: 10.6023/cjoc201912006
	(c) Xu, W.; Huang, D.; Wang, K.; Zhao, F.; Zhao, Z.; Hu, Y.; Su, Y.; Hu, Y. Chin. J. Org. Chem. 2020, 40, 922. (in Chinese) doi: 10.6023/cjoc201910011
	(徐炜刚, 黄丹凤, 王克虎, 赵芳霞, 赵转霞, 虎永琴, 苏瀛鹏, 胡雨来, 有机化学, 2020, 40, 922.) doi: 10.6023/cjoc201910011
[20]	(a) Peng, X.; Huang, D.; Wang, K. H.; Wang, Y.; Wang, J.; Su, Y.; Hu, Y. Org. Biomol. Chem. 2017, 15, 6214. doi: 10.1039/C7OB01299C
	(b) Liu, L.; Huang, D.; Wang, Y.; Wen, L.; Yang, Z.; Su, Y.; Wang, K.; Hu, Y. Chin. J. Org. Chem. 2018, 38, 1469. (in Chinese) doi: 10.6023/cjoc201712036
	(刘丽丽, 黄丹凤, 王玉祥, 文岚, 杨政, 苏瀛鹏, 王克虎, 胡雨来, 有机化学, 2018, 38, 1469.) doi: 10.6023/cjoc201712036
	(c) Wen, L.; Huang, D.; Wang, K.-H.; Wang, Y.; Liu, L.; Yang, Z.; Su, Y.; Hu, Y. Synthesis 2018, 50, 1979. doi: 10.1055/s-0036-1591768
	(d) Zhao, F.; Wang, K. H.; Wen, L.; Zhao, Z.; Hu, Y.; Xu, W.; Huang, D.; Su, Y.; Wang, J.; Hu, Y. Asian J. Org. Chem. 2020, 9, 1036. doi: 10.1002/ajoc.202000057
[21]	(a) Gao, M.; He, C.; Chen, H.; Bai, R.; Cheng, B.; Lei, A. Angew. Chem., Int. Ed. 2013, 52, 6958. doi: 10.1002/anie.201302604
	(b) Wang, Z.; Wu, Q.; Jiang, J.; Li, Z.; Peng, X.; Shao, P.; He, Y. Org. Chem. Front. 2018, 5, 36. doi: 10.1039/C7QO00692F
[22]	(a) Nakamura, S.; Maeno, Y.; Ohara, M.; Yamamura, A.; Funahashi, Y.; Shibata, N. Org. Lett. 2012, 14, 2960. doi: 10.1021/ol301256q pmid: 22656050
	(b) Tamura, K.; Kumagai, N.; Shibasaki, M. Eur. J. Org. Chem. 2015, 2015, 3026. doi: 10.1002/ejoc.201500336 pmid: 22656050
[23]	(a) Shi, Z.; Yu, P.; Chua, P. J.; Zhong, G. Adv. Synth. Catal. 2009, 351, 2797. doi: 10.1002/adsc.200900580
	(b) Viso, A.; Fernandez de la Pradilla, R.; Tortosa, M.; Garcia, A.; Flores, A. Chem. Rev. 2011, 111, PR1. doi: 10.1021/cr100127y
[24]	(a) Grigg, R.; Lansdell, M. I.; Thornton-Pett, M. Tetrahedron 1999, 55, 2025. doi: 10.1016/S0040-4020(98)01216-2
	(b) Liu, J.; Fang, Z.; Zhang, Q.; Liu, Q.; Bi, X. Angew. Chem., Int. Ed. 2013, 52, 5953.
	(c) Abás, S.; Estarellas, C.; Javier Luque, F.; Escolano, C. Tetrahedron 2015, 71, 2872. doi: 10.1016/j.tet.2015.03.065
	(d) Qiao, S.; Wilcox, C. B.; Unruh, D. K.; Jiang, B.; Li, G. J. Org. Chem. 2017, 82, 2992. doi: 10.1021/acs.joc.6b03068

Entry	Mole ratio of 1a/2a/catalyst/base	Catalyst	Base	Solvent	Time/h	Isolated yield/%
1	1∶2∶0∶2	—	DBU	CHCl₃	72	35
2	1∶2∶0.2∶0	CuI	—	CHCl₃	12	0
3	1∶2∶0.2∶0.2	CuI	DBU	CHCl₃	12	80
4	1∶2.5∶0.2∶0.2	CuI	DBU	CHCl₃	12	70
5	1∶1.5∶0.2∶0.2	CuI	DBU	CHCl₃	12	74
6	1∶2∶0.2∶0.2	CuI	DBU	CH₂Cl₂	12	50
7	1∶2∶0.2∶0.2	CuI	DBU	DCE	12	76
8	1∶2∶0.2∶0.2	CuI	DBU	EtOH	12	45
9	1∶2∶0.2∶0.2	CuI	DBU	CH₃CN	12	40
10	1∶2∶0.2∶0.2	CuI	DBU	Toluene	12	73
11	1∶2∶0.2∶0.2	CuI	DBU	1,4-Dioxane	12	76
12	1∶2∶0.2∶0.2	CuI	DBU	THF	12	82
13	1∶2∶0.2∶0.2	CuI	DBU	THF	7	85
14	1∶2∶0.2∶0.2	CuI	Et₃N	THF	72	0
15	1∶2∶0.2∶0.2	CuI	DABCO	THF	72	0
16	1∶2∶0.2∶0.2	CuI	K₂CO₃	THF	72	20
17	1∶2∶0.2∶0.2	CuI	Na₂CO₃	THF	72	25
18	1∶2∶0.2∶0.2	CuI	Cs₂CO₃	THF	72	13
Entry	Mole ratio of 1a/2a/catalyst/base	Catalyst	Base	Solvent	Time/h	Isolated yield/%
19	1∶2∶0.2∶0.2	Ag₂CO₃	DBU	THF	1	88
20	1∶2∶0.2∶0.2	AgOAc	DBU	THF	40 min	90
21	1∶2∶0.2∶0.2	AgOTf	DBU	THF	2	88
22	1∶2∶0.2∶0.2	Ag₂O	DBU	THF	1	86
23	1∶2∶0.2∶0.2	AgNO₃	DBU	THF	3	61
24	1∶2∶0.2∶0	AgOAc	—	THF	40 min	90
25	1∶2∶0.1∶0	AgOAc	—	THF	40 min	26

Entry	Mole ratio of 1a/2a/catalyst/base	Catalyst	Base	Solvent	Time/h	Isolated yield/%
1	1∶2∶0∶2	—	DBU	CHCl₃	72	35
2	1∶2∶0.2∶0	CuI	—	CHCl₃	12	0
3	1∶2∶0.2∶0.2	CuI	DBU	CHCl₃	12	80
4	1∶2.5∶0.2∶0.2	CuI	DBU	CHCl₃	12	70
5	1∶1.5∶0.2∶0.2	CuI	DBU	CHCl₃	12	74
6	1∶2∶0.2∶0.2	CuI	DBU	CH₂Cl₂	12	50
7	1∶2∶0.2∶0.2	CuI	DBU	DCE	12	76
8	1∶2∶0.2∶0.2	CuI	DBU	EtOH	12	45
9	1∶2∶0.2∶0.2	CuI	DBU	CH₃CN	12	40
10	1∶2∶0.2∶0.2	CuI	DBU	Toluene	12	73
11	1∶2∶0.2∶0.2	CuI	DBU	1,4-Dioxane	12	76
12	1∶2∶0.2∶0.2	CuI	DBU	THF	12	82
13	1∶2∶0.2∶0.2	CuI	DBU	THF	7	85
14	1∶2∶0.2∶0.2	CuI	Et₃N	THF	72	0
15	1∶2∶0.2∶0.2	CuI	DABCO	THF	72	0
16	1∶2∶0.2∶0.2	CuI	K₂CO₃	THF	72	20
17	1∶2∶0.2∶0.2	CuI	Na₂CO₃	THF	72	25
18	1∶2∶0.2∶0.2	CuI	Cs₂CO₃	THF	72	13
Entry	Mole ratio of 1a/2a/catalyst/base	Catalyst	Base	Solvent	Time/h	Isolated yield/%
19	1∶2∶0.2∶0.2	Ag₂CO₃	DBU	THF	1	88
20	1∶2∶0.2∶0.2	AgOAc	DBU	THF	40 min	90
21	1∶2∶0.2∶0.2	AgOTf	DBU	THF	2	88
22	1∶2∶0.2∶0.2	Ag₂O	DBU	THF	1	86
23	1∶2∶0.2∶0.2	AgNO₃	DBU	THF	3	61
24	1∶2∶0.2∶0	AgOAc	—	THF	40 min	90
25	1∶2∶0.1∶0	AgOAc	—	THF	40 min	26