可见光驱动1,3-烯炔与4-酰基二氢吡啶的串联环化反应合成氮杂芳烃官能团化的多取代呋喃

doi:10.6023/cjoc202509014

有机化学 ›› 2026, Vol. 46 ›› Issue (4): 1763-1775.DOI: 10.6023/cjoc202509014 上一篇下一篇

研究论文

可见光驱动1,3-烯炔与4-酰基二氢吡啶的串联环化反应合成氮杂芳烃官能团化的多取代呋喃

王光辉^a^,^†, 王冰辉^b^,^†, 班旭^a^,^*(), 赵筱薇^c^,^*(), 江智勇^a^,^d^,^*()

^a 河南师范大学化学化工学院河南新乡 453007
^b 漯河医学高等专科学校河南省特医食品工程技术研究中心河南省特医食品工程技术研究中心河南漯河 462000
^c 河南大学药学院河南开封 475004
^d 南京大学化学化工学院配位化学国家重点实验室配位化学国家重点实验室南京 210093

收稿日期:2025-10-02 修回日期:2025-10-28 发布日期:2025-11-19
通讯作者: 班旭, 赵筱薇, 江智勇
作者简介:
^†共同第一作者.
基金资助:
国家自然科学基金(22301061); 国家自然科学基金(22171072); 国家自然科学基金(22201068); 国家自然科学基金(22471064); 国家自然科学基金(22401086); 河南省自然科学基金重点项目(252300421286); 河南省自然科学基金重点项目(254000510005); 河南省科学技术厅科学技术研究项目(252102310409); 漯河医学高等专科学校博士科研启动基金(2024-DF-04); 南京大学化学化工学院配位化学国家重点实验室开放研究基金资助项目.

Visible Light-Driven Tandem Cyclization Reactions of 1,3-Eneynes with 4-Acyl-dihydropyridines to Access Azaarene-Functionalized Polysubstituted Furans

Guanghui Wang^a, Binghui Wang^b, Xu Ban^a^,^*(), Xiaowei Zhao^c^,^*(), Zhiyong Jiang^a^,^d^,^*()

^a School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, Henan 453007
^b Henan Province Engineering & Technology Research Center of Foods for Special Medical Purpose, Luohe Medical College, Luohe, Henan 462000
^c College of Pharmacy, Henan University, Kaifeng, Henan 475004
^d State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093

Received:2025-10-02 Revised:2025-10-28 Published:2025-11-19
Contact: Xu Ban, Xiaowei Zhao, Zhiyong Jiang
About author:
^†These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22301061); National Natural Science Foundation of China(22171072); National Natural Science Foundation of China(22201068); National Natural Science Foundation of China(22471064); National Natural Science Foundation of China(22401086); Key Project of the Henan Provincial Natural Science Foundation(252300421286); Key Project of the Henan Provincial Natural Science Foundation(254000510005); Science and Technology Research Project of Henan Provincial Department of Science and Technology(252102310409); Doctoral Scientific Research Start-Up Foundation of Luohe Medical College(2024-DF-04); Open Research Fund of State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University.

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摘要/Abstract

建立了一种可见光驱动、Brønsted酸促进的1,3-烯炔与4-酰基-1,4-二氢吡啶(4-acyl-DHPs)串联环化反应, 实现了氮杂芳烃官能团化的多取代呋喃的高效合成. 该无金属合成策略在温和条件下进行, 具有较广的底物适用范围, 可兼容含有复杂药物结构的烯炔底物及多种酰基自由基前体. 机理研究表明, 反应经历了自由基-阴离子-质子化的连续过程, 包含酰基自由基加成、联烯中间体形成以及Brønsted酸促进的环异构化过程. 该方法具有模块化和环境友好的特点, 可高效构筑含杂芳烃片段的多功能化呋喃, 并表现出优异的官能团耐受性.

关键词: 可见光, 光反应, 多取代呋喃, 串联反应, 1,3-烯炔

A visible-light-driven, Brønsted-Lowry acids-promoted cascade cyclization between 1,3-enynes and 4-acyl-1,4- dihydropyridines (4-acyl-DHPs) has been established for the efficient synthesis of azaarene-functionalized polysubstituted furans. This metal-free transformation proceeds under mild reaction conditions and exhibits a broad substrate scope, encom- passing complex drug-derived enynes and diverse acyl radical precursors. Mechanistic investigations support a reaction pathway involving a radical-anionic-protonation sequence, including acyl radical addition, allene formation, and Brønsted- Lowry acids-facilitated cycloisomerization. The methodology offers a modular and environmentally benign route to azaarene- containing, densely functionalized furans with excellent functional group compatibility.

Key words: visible light, photoreaction, poly-substituted furan, cascade reaction, 1,3-eneynes

引用此文

王光辉, 王冰辉, 班旭, 赵筱薇, 江智勇. 可见光驱动1,3-烯炔与4-酰基二氢吡啶的串联环化反应合成氮杂芳烃官能团化的多取代呋喃[J]. 有机化学, 2026, 46(4): 1763-1775.

Guanghui Wang, Binghui Wang, Xu Ban, Xiaowei Zhao, Zhiyong Jiang. Visible Light-Driven Tandem Cyclization Reactions of 1,3-Eneynes with 4-Acyl-dihydropyridines to Access Azaarene-Functionalized Polysubstituted Furans[J]. Chinese Journal of Organic Chemistry, 2026, 46(4): 1763-1775.

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[1]	(a) Lipshutz, B. H. Chem. Rev. 1986, 86, 795.
	(b) Sperry, J. B.; Wright, D. L. Curr. Opin. Drug Discovery Dev. 2005, 8, 723.
	(c) Boto, A.; Alvarez, L. Furan and Its Derivatives from Heterocycles in Natural Product Synthesis, Wiley-VCH Verlag GmbH& Co. KGaA, Weinheim, 2011, pp. 97-152.
	(d) Alnabulsi, S.; Hussein, B.; Santina, E. Bioorg. Med. Chem. Lett. 2018, 28, 1292.
[2]	(a) Zhang, W.; Xu, W.; Zhang, F.; Li, Y. Chin. J. Org. Chem. 2019, 39, 1277 (in Chinese).
	(张文生, 许文静, 张斐, 李焱, 有机化学, 2019, 39, 1277.)
	(b) Mohapatra, S.; Panda, J.; Mohapatra, S.; Nayak, S. Asian J. Org. Chem. 2023, 12, e202300304.
[3]	Amarnath, V.; Amarnath, K. J. Org. Chem. 1995, 60, 301.
[4]	Mross, G.; Holtz, E.; Langer, P. J. Org. Chem. 2006, 71, 8045.
[5]	(a) Ma, S.; Lu, L.; Zhang, J. J. Am. Chem. Soc. 2004, 126, 9645.
	(b) Xia, Y.; Xia, Y.; Ge, R. Angew. Chem., Int. Ed. 2014, 53, 3917.
[6]	Yao, T.; Zhang, X.; Larock, R. C. J. Am. Chem. Soc. 2004, 126, 11164.
[7]	(a) Wang, L.; Liu, X.; Wang, M.; Liu, J. Org. Lett. 2016, 18, 2162.
	(b) Zhang, G.; Cai, X.; Jia, J.; Feng, B.; Yang, K.; Song, Q. ACS Catal. 2023, 13, 9502.
	(c) Zhang, W.; Li, Z.; Hu, H.; Wang, J.; Xu, Z. F.; Yu, M.; Li, C. Y. Org. Lett. 2024, 26, 5453.
[8]	(a) Xiao, Y.; Zhang, J. Angew. Chem., Int. Ed. 2008, 47, 1903.
	(b) Xia, Y.; Qu, S.; Xiao, Q.; Wang, Z. X.; Qu, P.; Chen, L.; Liu, Z.; Tian, L.; Huang, Z.; Zhang, Y.; Wang, J. J. Am. Chem. Soc. 2013, 135, 13502.
	(c) Hao, J.; Guo, X.; He, S.; Xu, Z.; Chen, L.; Li, Z.; Yang, W. Nat. Commun. 2021, 12, 1304.
[9]	(a) Gao, H.; Zhang, J. Chem. Eur. J. 2012, 18, 2777.
	(b) Cho, H.-J.; Kim, Y. L.; Kim, J. H. J. Org. Chem. 2022, 87, 16424.
[10]	(a) Mao, S.; Tang, L.; Wu, C.; Tu, X.; Gao, Q.; Deng, G. Org. Lett. 2019, 21, 2416.
	(b) Peng, H.; Zhang, Y.; Deng, G. J. Org. Chem. 2023, 88, 7038.
[11]	Li, L.; Kail, S.; Weber, S. M.; Hilt, G. Angew. Chem., Int. Ed. 2021, 60, 23661.
[12]	(a) Fatheree, P. R.; McKinnell, R. M. US 20110178101, 2011.
	(b) Liang, G.; Aldous, S.; Merriman, G.; Levell, J.; Pribish, J.; Cairns, J.; Pauls, H. W. Bioorg. Med. Chem. Lett. 2012, 22, 1049.
	(c) Yao, Z.; Deng, W.; Xu, Y.CN 106939027, 2017 (in Chinese).
[13]	(a) Jiang, H.; Cheng, Y.; Yu, S. Org. Lett. 2013, 15, 4884.
	(b) Walker, J. C. L.; Werrel, S.; Donohoe, T. J. Chem.-Eur. J. 2019, 25, 13114.
	(c) Murray, P. R. D.; Leibler, I. N.-M.; Hell, S. M.; Villalona, E.; Doyle, A. G.; Knowles, R. ACS Catal. 2022, 12, 13732.
	(d) Mondal, S.; Mondal, S.; Midya, S. P.; Das, S.; Mondal, S.; Ghosh, P. Org. Lett. 2023, 25, 184.
[14]	Sun, Y.; Zhang, N.; Ren, J.; Huang, H.; Luan, X.; Zuo, Z. Org. Lett. 2024, 26, 35.
[15]	(a) Lv, X.; Xu, H.; Yin, Y.; Zhao, X.; Jiang, Z. Chin. J. Chem. 2020, 38, 1480.
	(b) Yin, Y.; Zhao, X.; Jiang, Z. ChemCatChem 2020, 12, 4471.
	(c) Ban, X.; Jiang, Z. In Comprehensive Chirality, 2nd ed., Ed.: Cossy, J., Elsevier, Academic Press, Amsterdam, Netherlands, 2024, p. 50.
[16]	Hu, W.; Zhan, Q.; Zhou, H.; Cao, S.; Jiang, Z. Chem. Sci. 2021, 12, 6543.
[17]	Goti, G.; Bieszczad, B.; Penaloza, V. A.; Melchiorre, P. Angew. Chem., Int. Ed. 2019, 58, 1213.
[18]	He, X.-K; Lu, J.; Zhang, A.-J.; Zhang, Q.-Q.; Xu, G.-Y.; Xuan, J. Org. Lett. 2020, 22, 5984.
[19]	Wang, P.-Z.; Chen, J.-R.; Xiao, W.-J. Org. Biomol. Chem. 2019, 17, 6936.
[20]	Bieszczad, B.; Perego, L. A.; Melchiorre, P. Angew. Chem., Int. Ed. 2019, 58, 16878.
[21]	Vanitcha, A.; Gontard, G.; Vanthuyne, N.; Derat, E.; Mouriès‐ Mansuy, V.; Fensterbank, L. Adv. Synth. Catal. 2015, 357, 2213.
[22]	Pathipati, S. R.; van der Werf, A.; Selander, N. Org. Lett. 2018, 20, 3691.
[23]	Yao, S.; Zhao, X.; Ban, X.; Shao, T.; Yin, Y.; Hu, W.; Jiang, Z. Org. Chem. Front. 2023, 10, 4779.
[24]	Li, M.; Zhu, X.-Y.; Qiu, Y.-F.; Han, Y.-P.; Xia, Y.; Wang, C.-T.; Li, X.-S.; Wei, W.-X.; Liang, Y.-M. Adv. Synth. Catal. 2019, 361, 2945.
[25]	Datta, S.; Odedra, A.; Liu, R. S. J. Am. Chem. Soc. 2005, 127, 11606.
[26]	Yang, J.; Zhang, P.; Shen, Z.; Zhou, Y.; Yu, Z.-X. Chem 2023, 9, 1477.
[27]	Wang, G.; Li, L.; Jiang, Y.; Zhao, X.; Ban, X.; Shao, T.; Yin, Y; Jiang, Z. Angew. Chem., Int. Ed. 2023, 62, e202214838.
[28]	Pünner, F.; Hilt, G. Chem. Commun. 2012, 48, 3617.
[29]	Barrero, A. F.; Herrador, M. M.; Quilez del Moral, J. F.; Arteaga, P.; Arteaga, J. F.; Diéguez, H. R.; Sánchez, E. M. J. Org. Chem. 2007, 72, 2988.

Entry	Brønsted-Lowry acid	Solvent	Yield^b/%
1	None	CH₂Cl₂	16
2	TsOH (10 mol%)	CH₂Cl₂	41
3	AcOH (10 mol%)	CH₂Cl₂	36
4	H₂NSO₃H (10 mol%)	CH₂Cl₂	23
5	TfOH (10 mol%)	CH₂Cl₂	0
6	(PhO)₂PO₂H (10 mol%)	CH₂Cl₂	62
7	(PhO)₂PO₂H (10 mol%)	DCE	59
8^c	(PhO)₂PO₂H (10 mol%)	THF	60
9	(PhO)₂PO₂H (10 mol%)	Toluene	57
10	(PhO)₂PO₂H (10 mol%)	CH₃CN	55
11	(PhO)₂PO₂H (10 mol%)	CHCl₃	48
12	(PhO)₂PO₂H (10 mol%)	Et₂O	51
13	(PhO)₂PO₂H (10 mol%)	Acetone	59
14	(PhO)₂PO₂H (30 mol%)	CH₂Cl₂	74
15	(PhO)₂PO₂H (50 mol%)	CH₂Cl₂	85
16	(PhO)₂PO₂H (60 mol%)	CH₂Cl₂	84
17^c	(PhO)₂PO₂H (50 mol%)	CH₂Cl₂	n.p.
18^d	(PhO)₂PO₂H (50 mol%)	CH₂Cl₂	n.p.

Entry	Brønsted-Lowry acid	Solvent	Yield^b/%
1	None	CH₂Cl₂	16
2	TsOH (10 mol%)	CH₂Cl₂	41
3	AcOH (10 mol%)	CH₂Cl₂	36
4	H₂NSO₃H (10 mol%)	CH₂Cl₂	23
5	TfOH (10 mol%)	CH₂Cl₂	0
6	(PhO)₂PO₂H (10 mol%)	CH₂Cl₂	62
7	(PhO)₂PO₂H (10 mol%)	DCE	59
8^c	(PhO)₂PO₂H (10 mol%)	THF	60
9	(PhO)₂PO₂H (10 mol%)	Toluene	57
10	(PhO)₂PO₂H (10 mol%)	CH₃CN	55
11	(PhO)₂PO₂H (10 mol%)	CHCl₃	48
12	(PhO)₂PO₂H (10 mol%)	Et₂O	51
13	(PhO)₂PO₂H (10 mol%)	Acetone	59
14	(PhO)₂PO₂H (30 mol%)	CH₂Cl₂	74
15	(PhO)₂PO₂H (50 mol%)	CH₂Cl₂	85
16	(PhO)₂PO₂H (60 mol%)	CH₂Cl₂	84
17^c	(PhO)₂PO₂H (50 mol%)	CH₂Cl₂	n.p.
18^d	(PhO)₂PO₂H (50 mol%)	CH₂Cl₂	n.p.

可见光驱动1,3-烯炔与4-酰基二氢吡啶的串联环化反应合成氮杂芳烃官能团化的多取代呋喃

Visible Light-Driven Tandem Cyclization Reactions of 1,3-Eneynes with 4-Acyl-dihydropyridines to Access Azaarene-Functionalized Polysubstituted Furans

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