可回收铋配合物催化氮亲核试剂与对醌甲基化物1,6-加成:轻松获得N-杂环取代的不对称三芳基甲烷衍生物

doi:10.6023/cjoc202109026

有机化学 ›› 2022, Vol. 42 ›› Issue (3): 796-802.DOI: 10.6023/cjoc202109026 上一篇下一篇

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可回收铋配合物催化氮亲核试剂与对醌甲基化物1,6-加成:轻松获得N-杂环取代的不对称三芳基甲烷衍生物

刘冬兰, 许海燕^*(), 杭懿, 陆鸿飞^*()

江苏科技大学环境与化学工程学院江苏镇江 212100

收稿日期:2021-09-17 修回日期:2021-11-08 发布日期:2021-11-25
通讯作者: 许海燕, 陆鸿飞
作者简介:
† 共同第一作者
基金资助:
国家自然科学基金(21901087); 江苏省自然科学基金(BK20190591)

1,6-Addition of Nitrogen Nucleophile to para-Quinone Methides Catalyzed by Recyclable Bismuth Complex: Facile Access to N-Heterocyclic Substituted Unsymmetric Triarylmethane Derivatives

Donglan Liu, Haiyan Xu(), Yi Hang, Hongfei Lu()

School of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang, Jiangsu 212100

Received:2021-09-17 Revised:2021-11-08 Published:2021-11-25
Contact: Haiyan Xu, Hongfei Lu
About author:
† These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(21901087); Natural Science Foundation of Jiangsu Province(BK20190591)

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摘要/Abstract

开发了一种用对醌甲基化物(p-QMs)和各种芳香族N-杂环化合物1,6-氮杂-迈克尔加成合成含氮不对称三芳基甲烷衍生物的方法. 这种合成方法具有反应条件温和、催化剂负载量可接受、原子经济性、易于放大的特点, 并且能够以中等至优异的产率形成N-杂环取代的不对称三芳基甲烷衍生物. 此外, 铋催化剂可以重复使用多次而不会损失其活性.

关键词: 可回收的铋催化剂, N-杂环取代的不对称三芳基甲烷衍生物, 对醌甲基化物, 1,6-迈克尔加成反应

A useful protocol for the synthesis of nitrogen-containing unsymmetric triarylmethane derivatives through 1,6-aza-Michael addition of para-quinone methides (p-QMs) and various aromatic N-heterocycles was developed. This established synthetic strategy features mild reaction conditions, acceptable catalyst loading, atom economy, easy scale-up and enables the formation of N-heterocyclic-substituted unsymmetric triarylmethane derivatives in moderate to excellent yields. Moreover, the bismuth catalyst can be reused several times without losing of its activity.

Key words: recyclable bismuth catalyst, N-heterocyclic-substituted unsymmetric triarylmethane derivatives, para-quinone methide, 1,6-Michael addition reaction

引用此文

刘冬兰, 许海燕, 杭懿, 陆鸿飞. 可回收铋配合物催化氮亲核试剂与对醌甲基化物1,6-加成:轻松获得N-杂环取代的不对称三芳基甲烷衍生物[J]. 有机化学, 2022, 42(3): 796-802.

Donglan Liu, Haiyan Xu, Yi Hang, Hongfei Lu. 1,6-Addition of Nitrogen Nucleophile to para-Quinone Methides Catalyzed by Recyclable Bismuth Complex: Facile Access to N-Heterocyclic Substituted Unsymmetric Triarylmethane Derivatives[J]. Chinese Journal of Organic Chemistry, 2022, 42(3): 796-802.

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图/表 7

Entry	Catalyst	Solvent	Yield^b/%
1	—	CH₃CN	trace
2^c	[Bi]	CH₃CN	91
3	BiCl₃	CH₃CN	80
4	Bi(OTf)₃	CH₃CN	82
5	FeCl₃	CH₃CN	86
6	AlCl₃	CH₃CN	85
7	Sc(OTf)₃	CH₃CN	82
8	Ni(OTf)₂	CH₃CN	14
9	Zn(OTf)₂	CH₃CN	87
10	[Bi]	MeOH	55
11	[Bi]	1,4-Dioxane	77
12	[Bi]	Toluene	10
13	[Bi]	DCM	85
14	[Bi] (1 mol%)	CH₃CN	80

Table 1. Conditions screeninga

Figure 1. Structure of catalyst

Table 2. Substrate scope of p-quinone methides 1a～1l with pyrazole 2aa

Table 3. Substrate scope of N-heterocycles (2) with p-QMs (1a) under the optimized reaction condi-tions

Scheme 1. Gram-scale experiments

Figure 2. Recycling Catalyst (C5H6N4O)(C5H5N4O)3(C5H4- N4O)[Bi2Cl11]Cl2

Scheme 3. Proposed mechanism

参考文献 10

[1]	Gao, S.; Xu, X. Y.; Yuan, Z. B.; Zhou, H. P.; Yao, H. Q.; Lin, A. J. Eur. J. Org. Chem. 2016, 3006.
[2]	(a) Shirakawa, S.; Kobayashi, S. Org. Lett. 2006, 8, 4939. pmid: 32307478
	(b) Kumar, S.; Malik, V.; Kaur, N.; Kaur, K. Tetrahedron Lett. 2006, 47, 8483. doi: 10.1016/j.tetlet.2006.09.158 pmid: 32307478
	(c) He, Q. L.; Sun, F. L.; Zheng, X. J.; You, S. L. Synlett. 2009, 1111. pmid: 32307478
	(d) Kim, Y.; Kwon, Y. I.; Kim, S. G. Synthesis. 2020, 52, 281. doi: 10.1055/s-0039-1690731 pmid: 32307478
	(e) Tuengpanya, S.; Chantana, C.; Sirion, U.; Siritanyong, W.; Srisook, K. Tetrahedron. 2018, 74, 4373. doi: 10.1016/j.tet.2018.05.079 pmid: 32307478
	(f) Zhou, T.; Li, S. H.; Huang, B.; Li, C.; Zhao, Y.; Chen, J. Q.; Chen, A. L.; Xiao, Y. J.; Liu, L.; Zhang, J. L. Org. Biomol. Chem. 2017, 15, 4941. doi: 10.1039/c7ob00911a pmid: 32307478
	(g) Rodrigues, S. M. M.; Previdi, D.; Baviera, G. S.; Matias, A. A.; Donate, P. M. Synthesis. 2019, 51, 4498. doi: 10.1055/s-0037-1610727 pmid: 32307478
	(h) Beltrá, J.; Gimeno, M. C.; Herrera, R. P. Beilstein J. Org. Chem. 2014, 10, 2206. doi: 10.3762/bjoc.10.228 pmid: 32307478
	(i) Dhiman, S.; Ramasastry, S. S. V. Org. Biomol. Chem. 2013, 11, 8030. doi: 10.1039/c3ob41945b pmid: 32307478
	(a) Yu, J. Y.; Kuwano, R. Org. Lett. 2008, 10, 973. doi: 10.1021/ol800078j pmid: 32307478
	(b) Taylor, B. L. H.; Harris, M. R.; Jarvo, E. R. Angew. Chem., Int. Ed. 2012, 51, 1. pmid: 32307478
	(c) Wang, Z. H.; Zhu, Y. S.; Pan, X. G.; Wang, G.; Liu, L. Angew. Chem., Int. Ed. 2020, 59, 3053. doi: 10.1002/anie.v59.8 pmid: 32307478
	(d) Yim, J. C.-H.; Nambo, M.; Tahara, Y.; Crudden, C. M. Chem. Lett. 2019, 48, 975. doi: 10.1246/cl.190334 pmid: 32307478
	(a) Kumaran, S.; Prabhakaran, M.; Mariyammal, N.; Parthasarathy, K. Org. Biomol. Chem. 2020, 18, 7837. doi: 10.1039/D0OB01789B pmid: 32307478
	(b) Huang, G. B.; Huang, W. H.; Guo, J.; Xu, D. L.; Qu, X. C.; Zhai, P. H.; Zheng, X. H.; Weng, J.; Lu, G. Adv. Synth. Catal. 2019, 361, 1241. doi: 10.1002/adsc.v361.6 pmid: 32307478
	(c) Jillella, R.; Oh, D. H; Oh, C. H. New J. Chem. 2018, 42, 16886. doi: 10.1039/C8NJ03955K pmid: 32307478
	(d) Rayaroth, A.; Singh, R. K.; Kalyanakrishnan, A. V.; Hari, K.; Kaliyamoorthy, A. Org. Biomol. Chem. 2020, 18, 3354. doi: 10.1039/d0ob00419g pmid: 32307478
[3]	Guin, S.; Saha, H. K.; Patel, A. K.; Gudimella, S. K.; Biswas, S.; Samanta, S. Tetrahedron. 2020, 76, 131338. doi: 10.1016/j.tet.2020.131338
[4]	Wang, L.; Wang, N.; Qi, Y.; Sun, S. T.; Liu, X. G.; Li, W.; Liu, L. Chin. J. Org. Chem. 2020, 40, 3934. doi: 10.6023/cjoc202004027
	(a) Luo, J. F.; Wei, W, T. Adv. Synth. Catal. 2018, 360, 2076. doi: 10.1002/adsc.v360.11
	(b) Bhunia, S.; Pawar, G, G.; Kumar, S. V.; Jiang, Y.W.; Ma, D. W. Angew. Chem., Int. Ed. 2017, 56, 16136. doi: 10.1002/anie.v56.51
[5]	Wang, J. Y.; Hao, W. J.; Tu, S. J.; Jiang, B. Org. Chem. Front. 2020, 7, 1743. doi: 10.1039/D0QO00387E
[6]	Arde, P.; Anand, R. V. RSC Adv. 2016, 6, 77111. doi: 10.1039/C6RA11116E
[7]	Ma, Y. G.; Pang, J. X.; Pan, X. G.; Ma, S. T.; Liu, X. G.; Liu, L. Synlett 2020, 31, 1619. doi: 10.1055/s-0040-1706408
[8]	Wang, D. L.; Kan, L. L.; Ma, Y. D.; Liu, L. Chin. J. Org. Chem. 2021, 41, 3192. doi: 10.6023/cjoc202104003
[9]	Liang, X. H.; Xu, H. Y.; Li, H. L.; Chen, L.Z.; Lu, H. F. Eur. J. Org. Chem. 2020, 2020, 217. doi: 10.1002/ejoc.201901732
[10]	Zhang, X.; Gu, X. Y.; Gao, Y. H.; Nie, S. P.; Lu, H. F. Appl. Organomet. Chem. 2017, 31, 3590.

可回收铋配合物催化氮亲核试剂与对醌甲基化物1,6-加成:轻松获得N-杂环取代的不对称三芳基甲烷衍生物

1,6-Addition of Nitrogen Nucleophile to para-Quinone Methides Catalyzed by Recyclable Bismuth Complex: Facile Access to N-Heterocyclic Substituted Unsymmetric Triarylmethane Derivatives

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