AlCl3催化3-(2-氨基乙基)吡咯的合成

doi:10.6023/cjoc202102011

有机化学 ›› 2021, Vol. 41 ›› Issue (6): 2335-2342.DOI: 10.6023/cjoc202102011 上一篇下一篇

研究论文

AlCl₃催化3-(2-氨基乙基)吡咯的合成

白冰^a^,^*(), 徐芳琳^a, 杨静^a, 张改红^a, 毛多斌^a, 王宁^b^,^*()

a 郑州轻工业大学食品与生物工程学院郑州 450000
b 河南卷烟工业烟草薄片有限公司河南许昌 461000

收稿日期:2021-02-01 修回日期:2021-03-02 发布日期:2021-03-22
通讯作者: 白冰, 王宁
基金资助:
河南省科技厅(192102110212)

Synthesis of 3-(2-Aminoethyl)pyrroles Catalyzed by AlCl₃

Bing Bai^a(), Fanglin Xu^a, Jing Yang^a, Gaihong Zhang^a, Duobin Mao^a, Ning Wang^b()

a School of Food & Biological Engineering, Zhengzhou University of Light Industry, Zhengzhou 450000
b Henan Cigarette Industrial Reconstituted Tobacco Sheet Co., Ltd., Xuchang, Henan 461000

Received:2021-02-01 Revised:2021-03-02 Published:2021-03-22
Contact: Bing Bai, Ning Wang
Supported by:
Department of Science and Technology of Henan Province(192102110212)

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摘要/Abstract

3-(2-氨基乙基)吡咯是形成6-氮杂吲哚骨架的重要中间体, 由于吡咯2位为高活性位点, 难以直接通过傅克反应合成3-(2-氨基乙基)吡咯. 报道了在吡咯α位引入拉电子基团, 形成对角β位的定位效应, 以无水AlCl₃为催化剂, 通过傅克反应在吡咯3位加成硝基烯烃, 进而得到取代的3-(2-氨基乙基)吡咯.

关键词: 三氯化铝, 3-(2-氨基乙基)吡咯, 6-氮杂吲哚

3-(2-Aminoethyl)pyrroles are important intermediates for the formation of the 6-azaindole skeleton. It was difficult

to synthesize 3-(2-aminoethyl)pyrroles from pyrrole by Friedel-Crafts alkylation directly because of the inactive site. The electron withdrawing groups were introduced at the α-position of pyrrole to form a positioning effect at the diagonal β-position. With anhydrous AlCl₃ as the catalyst, nitroalkenes could be added to the 3-position of pyrrole via Friedel-Crafts alkylation to obtain substituted 3-(2-aminoethyl)pyrroles.

Key words: Keywords aluminium chloride, 3-(2-aminoethyl)pyrrole, 6-azaindole

引用此文

白冰, 徐芳琳, 杨静, 张改红, 毛多斌, 王宁. AlCl₃催化3-(2-氨基乙基)吡咯的合成[J]. 有机化学, 2021, 41(6): 2335-2342.

Bing Bai, Fanglin Xu, Jing Yang, Gaihong Zhang, Duobin Mao, Ning Wang. Synthesis of 3-(2-Aminoethyl)pyrroles Catalyzed by AlCl₃[J]. Chinese Journal of Organic Chemistry, 2021, 41(6): 2335-2342.

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参考文献 16

[1]	Zhang, Y.; Zhao, Y. F.; Tebben, A, J.; Sheriff, S.; Ruzanov, M.; Mark P. Fereshteh, M. P.; Fan, Y.; Lippy, J.; Swanson, J.; Ho, C. P.; Wautlet, B. S.; Rose, A.; Parrish, K.; Yang, Z.; Donnell, A. F.; Zhang, L. P.; Fink, B. E.; Vite, G. D.; Augustine-Rauch, K.; Fargnoli, J.; Robert M. Borzilleri, R. M. ACS Med. Chem. Lett. 2018, 9,1117.
[2]	Guzii, A. G.; Makarieva, T. N.; Denisenko, V. A.; Gerasimenko, A. V.; Udovenko, A. A.; Popov, R. S.; Dmitrenok, P. S.; Golotin, V. A.; Fedorov, S. N.; Grebnev, B. B.; Stonik, V. A. J. Nat. Prod. 2019, 82,1704.
[3]	Merour, J. Y.; Routier, S.; Suzenet, F.; Joseph, B. Tetrahedron 2013, 69,4767.
[4]	Wucherer-Plietker, M.; Merkul, E.; Müller, T. J. J.; Esdar, C.; Knöchel, T.; Heinrich, T.; Buchstaller, H. P.; Greiner, H.; Dorsch, D.; Finsinger, D.; Calderini, M.; Bruge, D.; Grädler, U. Bioorg. Med. Chem. Lett. 2016, 26,3073.
[5]	(a) Mérour, J. Y.; Buron, F.; Plé, K.; Bonnet, P.; Routier, S. Molecules 2014, 19,19935.
	(b) Han, Y.; Dong, W.; Guo, Q. Q.; Li, X. F.; Huang, L. J. Eur. J. Med. Chem. 2020, 203,112506.
	(c) Motati, R. M.; Amaradhi, R.; Ganesh, T. Bioorg. Med. Chem. 2020, 28,115830.
	Ma, H. L.; Yan, X. J.; Xiao, Y. M.; Yuan, D. K.; Zhang, Z. H.; Fu, B.; Yuan, H. Z. Chin. J. Org. Chem. 2016, 36,158(in Chinese).
	(麻红利, 闫晓静, 肖玉梅, 袁德凯, 张振华, 傅滨, 袁会珠, 有机化学, 2016, 36,158.)
[6]	Ganser, C.; Lauermann, E.; Maderer, A.; Stauder, T.; Kramb, J. P.; Plutizki, S.; Kindler, T.; Moehler, M.; Dannhardt, G. J. Med. Chem. 2012, 55,9531.
[7]	Liu, Y. A.; Jin, Q. H.; Zou, Y. F.; Ding, Q.; Yan, S. S.; Wang, Z C.; Hao, X. S.; Nguyen, B.; Zhang, X. Y.; Pan, J. F.; Mo, T. T.; Jacobsen, K.; Lam, T.; Wu, T. Y-H.; Petrassi, H. M.; Bursulaya, B.; DiDonato, M.; Gordon, W. P.; Liu, B.; Baaten, J.; Hill, R.; Nguyen-Tran, V.; Qiu, M. H.; Zhang, Y.; Kamireddy, Q. A.; Espinola, S.; Deaton, L.; Ha, S.; Harb, G.; Jia, Y.; Li, J.; Shen, W. J.; Schumacher, A. M.; Colman, K.; Glynne, R.; Pan, S. F.; McNamara, P.; Laffitte, B.; Meeusen, S.; Molteni, V.; Loren, J. J. Med. Chem. 2020, 63,2958.
[8]	(a) Zhou, N. N.; Nowicka-Sans, B.; McAuliffe, B.; Ray, N.; Eggers, B.; Fang, H.; Fan, L.; Healy, M.; Langley, D. R.; Hwang, C.; Lataillade, M.; Hanna, G. J.; Krystal, M. J. Antimicrob. Chemother. 2014, 69,573.
	(b) Chen, K.; Risatti, C.; Bultman, M.; Soumeillant, M.; Simpson, J.; Zheng, B.; Fanfair, D.; Mahoney, D.; Mudryk, B.; Fox, R. J.; Hsaio, Y.; Murugesan, S.; Conlon, D. A.; Buono, F. G.; Eastgate, M. D. J. Org. Chem. 2014, 79,8757.
[9]	(a) Jeanty, M.; Blu, J.; Suzenet, F.; Guillaumet, G. Org. Lett. 2009, 11,5142.
	(b) Simmons, B. J.; Hoffmann, M.; Champagne, P. A.; Picazo, E.; Yamakawa, K.; Morrill, K. L.; Houk, K. N.; Garg, N. K. J. Am. Chem. Soc. 2017, 139,14833.
	(c) Alekseyev, R. S.; Amirova, S. R.; Terenin, V. I. Chem. Heterocycl. Compd. 2017, 53,196.
[10]	Zhang, Z. X.; Yang, Z.; Meanwell, N. A.; Kadow, J. F.; Wang, T. J. Org. Chem. 2002, 67,2345.
[11]	Osano, M.; Jhaveri, D. P.; Wipf, P. Org. Lett. 2020, 22,2215.
[12]	(a) Bultman, M. S.; Fan, J. Y.; Fanfair, D.; Soltani, M.; Simpson, J.; Murugesan, S.; Soumeillant, M.; Chen, K.; Risatti, C.; La Cruz, T. E.; Buono, F. G.; Hung, V.; Schild, R. L.; Ivy, S.; Sweeney, J. T.; Conlon, D. A.; Eastgate, M. D. Org. Process Res. Dev. 2017, 21,1131.
	(b) Huang, L.; Cai, Y.; Zheng, C.; Dai, L. X.; You, S. L. Angew. Chem., Int. Ed. 2017, 56,10545.
[13]	(a) Demopoulosv, V. J. J. Heterocycl. Chem. 1988, 25,635.
	(b) Lancianesi, S.; Palmieri, A.; Petrinia, M. Adv. Synth. Catal. 2013, 355,3285.
[14]	(a) Tu, Z. J.; Raju, B. R.; Liou, T. R.; Kavala, V.; Kuo, C. W.; Jang, Y. C.; Shih, Y. H.; Wang, C. C.; Yao, C. F. Tetrahedron 2009, 65,2436.
	(b) An, L. T.; Zou, J. P.; Zhang, L. L.; Zhang, Y. Tetrahedron Lett. 2007, 48,4297.
	Hua, Y. Z.; Han, X. W.; Huang, L. H.; Wang, M. C. Chin. J. Org. Chem. 2018, 38,237(in Chinese).
	(华远照, 韩兴旺, 黄利华, 王敏灿, 有机化学, 2018, 38,237.)
[15]	Meshram, H. M.; Kumar, D. A.; Reddy, B. C. Helv Chim. Acta 2009, 92,1002.
[16]	Nomiyama, S.; Ogura, T.; Ishida, H.; Aoki, K.; Tsuchimoto, T. J. Org. Chem. 2017, 82,5178.

Entry	Catalyst	Solvent	Yield^b/%
1	Y(CF₃SO₃)₃	CH₂Cl₂	0
2	La(CF₃SO₃)₃	CH₂Cl₂	0
3	Zn(OAc)₂	EtOH	0
4	FeCl₃	CH₂Cl₂	0
5	TiCl₄	CH₂Cl₂	0
6	BF₃•Et₂O	CH₂Cl₂	0
7	EtAlCl₂	CH₂Cl₂	65
8	AlCl₃	CH₂Cl₂	79
9	AlCl₃	C₂H₄Cl₂	67
10	AlCl₃	Benzene	Trace
11	AlCl₃	PhCl	30

Entry	Catalyst	Solvent	Yield^b/%
1	Y(CF₃SO₃)₃	CH₂Cl₂	0
2	La(CF₃SO₃)₃	CH₂Cl₂	0
3	Zn(OAc)₂	EtOH	0
4	FeCl₃	CH₂Cl₂	0
5	TiCl₄	CH₂Cl₂	0
6	BF₃•Et₂O	CH₂Cl₂	0
7	EtAlCl₂	CH₂Cl₂	65
8	AlCl₃	CH₂Cl₂	79
9	AlCl₃	C₂H₄Cl₂	67
10	AlCl₃	Benzene	Trace
11	AlCl₃	PhCl	30

Entry	AlCl₃/equiv.	Temp./℃	Time/h	Yield^b/%
1	1.0	r.t	16	57
2	2.0	r.t	16	79
3	3.0	r.t	10	87
4	4.0	r.t	10	82
5	3.0	0	24	62
6	3.0	–20	24	15
7	3.0	–40	24	0
8	3.0	–78	24	0
9	3.0	35	10	86
10	2.0	35	16	80

Entry	AlCl₃/equiv.	Temp./℃	Time/h	Yield^b/%
1	1.0	r.t	16	57
2	2.0	r.t	16	79
3	3.0	r.t	10	87
4	4.0	r.t	10	82
5	3.0	0	24	62
6	3.0	–20	24	15
7	3.0	–40	24	0
8	3.0	–78	24	0
9	3.0	35	10	86
10	2.0	35	16	80

Entry	R¹	R²	Time/h	3 (Yield^b/%)	[H]	4 (Yield^b/%)
1	CH₃	Ph	8	3a (87)	Pd/C, H₂	4a (79)
2	CH₃	4-MeC₆H₄	8	3b (88)	Pd/C, H₂	4b (80)
3	CH₃	2-FC₆H₄	6	3c (85)	Pd/C, H₂	4c (82)
4	CH₃	4-FC₆H₄	7	3d (83)	Pd/C, H₂	4d (84)
5	CH₃	4-ClC₆H₄	8	3e (85)	NaBH₄/NiCl₂	4e (78)
6	CH₃	4-BrC₆H₄	7	3f (87)	NaBH₄/NiCl₂	4f (70)
7	CH₃	4-MeOC₆H₄	8	3g (88)	Pd/C, H₂	4g (85)
8	CH₃	3-BrC₆H₄	6	3h (80)	NaBH₄/NiCl₂	4h (69)
9	CH₃	3,4-(MeO)₂C₆H₃	16	3i (61)^c	Pd/C, H₂	4i (81)
10	CH₃	2,4-Cl₂C₆H₃	7	3j(84)	NaBH₄/NiCl₂	4j (79)
11	CH₃CH₂	Ph	8	3k(86)	Pd/C, H₂	4k (83)
12	CH₃CH₂	3-BrC₆H₄	6	3l (82)	Pd/C, H₂	4l (71)

AlCl₃催化3-(2-氨基乙基)吡咯的合成

Synthesis of 3-(2-Aminoethyl)pyrroles Catalyzed by AlCl₃

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