NH4SCN-Promoted Formal [3＋3] Annulation for the Synthesis of 5-Arylated Pyrazolo[1,5-a]pyrimidines

doi:10.6023/cjoc202404017

Chinese Journal of Organic Chemistry ›› 2024, Vol. 44 ›› Issue (9): 2832-2840.DOI: 10.6023/cjoc202404017 Previous Articles Next Articles

ARTICLES

硫氰酸铵促进的[3＋3]环化反应合成5-芳基吡唑并[1,5-a]嘧啶

李龙龙^a, 何欣悦^a, 周龙生^a, 曲亨通^a, 冯承涛^a^,^*(), 徐坤^b^,^*()

a 安徽中医药大学药学院合肥 230012
b 北京工业大学化学与生命科学学院北京 100124

收稿日期:2024-04-11 修回日期:2024-05-07 发布日期:2024-05-23
通讯作者: 冯承涛, 徐坤
基金资助:
安徽省自然科学基金(2008085MB50); 及安徽省高校自然科学研究重点(KJ2021A0598)

NH₄SCN-Promoted Formal [3＋3] Annulation for the Synthesis of 5-Arylated Pyrazolo[1,5-a]pyrimidines

Longlong Li^a, Xinyue He^a, Longsheng Zhou^a, Hengtong Qu^a, Chengtao Feng^a(), Kun Xu^b()

a School of Pharmacy, Anhui University of Chinese Medicine, Hefei 230012
b College of Chemistry and Life Science, Beijing University of Technology, Beijing 100124

Received:2024-04-11 Revised:2024-05-07 Published:2024-05-23
Contact: Chengtao Feng, Kun Xu
Supported by:
Anhui Provincial Natural Science Foundation(2008085MB50); Education Bureau of Anhui Province(KJ2021A0598)

1. .pdf(3405KB)

Abstract

A formal [3＋3] annulation of 3-aminopyrazoles with cinnamaldehydes or cinnamyl alcohols mediated by NH₄SCN has been developed. This protocol provides a practical route to construct 5-arylated pyrazolo[1,5-a]pyrimidines with high functional group tolerance. The use of NH₄SCN as the cyanide anion surrogate allows the transient generation of cyanohydrin, which shifts the reactive center within cinnamaldehydes from formyl group to alkene group to realize an opposite regiocontrol comparing with previous reports.

Key words: tandem cyclization, hypervalent iodine, regioselectivity, pyrazolo[1,5-a]pyrimidine, cinnamaldehyde

Cite this article

Longlong Li, Xinyue He, Longsheng Zhou, Hengtong Qu, Chengtao Feng, Kun Xu. NH₄SCN-Promoted Formal [3＋3] Annulation for the Synthesis of 5-Arylated Pyrazolo[1,5-a]pyrimidines[J]. Chinese Journal of Organic Chemistry, 2024, 44(9): 2832-2840.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 7

References 16

[1]	(a) Kato, N.; Oka, M.; Murase, T.; Yoshida, M.; Sakairi, M.; Yamashita, S.; Yasuda, Y.; Yoshikawa, A.; Hayashi, Y.; Makino, M.; Takeda, M.; Mirensha, Y.; Kakigami, T. Bioorg. Med. Chem. 2011, 19, 7221.
	(b) Drev, M.; Groselj, U.; Mevec, S.; Pusavec, E.; Strekelj, J.; Golobic, A.; Dahmann, G.; Stanovnik, B.; Svete, J. Tetrahedron Lett. 2014, 70, 8267.
	(c) Hammouda, M. M.; Gaffer, H. E.; Elattar, K. M. RSC Med. Chem. 2022, 13, 1150.
	(d) Li, W.; Zhang, J.; Wang, M.; Dong, R.; Zhou, X.; Zheng, X.; Sun, L. Curr. Top. Med. Chem. 2022, 22, 284.
[2]	(a) Castillo, J. C.; Tigreros, A.; Portilla, J. J. Org. Chem. 2018, 83, 10887.
	(b) Tigreros, A.; Macías, M.; Portilla, J. Dyes Pigm. 2021, 184, 108730.
	(c) Ma, Y.; Chen, Y.; Lv, L.; Li, Z. Adv. Synth. Catal. 2021, 363, 1.
[3]	(a) Sun, J.; Qiu, J.-K.; Jiang, B.; Hao, W.-J.; Guo, C.; Tu, S.-J. J. Org. Chem. 2016, 81, 3321.
	(b) Al-Azmi, A. Curr. Org. Chem. 2019, 23, 721. doi: 10.2174/1385272823666190410145238
	(c) Elattar, K. M.; El-Mekabaty, A. Curr. Org. Synth. 2021, 18, 547.
	(d) Ma, Y. Y.; Chen, Y. J.; Lv, L. Y.; Li, Z. P. Adv. Synth. Catal. 2021, 363, 3233.
	(e) Arias-Gómez, A.; Portilla, A. J. Molecules 2021, 26, 2708.
[4]	Salem, M. A.; Helal, M. H.; Gouda, M. A.; EL-Gawad, H. H. A.; Shehab, M. A. M.; El-Khalafawy, A. Synth. Commun. 2019, 49, 1750.
[5]	(a) Sagar, R.; Park, S. B. J. Org. Chem. 2008, 73, 3270. doi: 10.1021/jo800190v pmid: 18351781
	(b) Kaswan, P.; Pericherla, K.; Purohit, D.; Kumar, A. Tetrahedron Lett. 2015, 56, 549. pmid: 18351781
[6]	(a) Abdel-Aziz, H. A.; Hamdy, N. A.; Fakhr, I. M. I.; Farag, A. M. Heterocycl. Chem. 2008, 45, 1033.
	(b) Martins, M. A. P.; Scapin, E.; Frizzo, C. F.; Rosa, F. A.; Bonacorso, H. G.; Zanatta, N. J. Braz. Chem. Soc. 2009, 20, 205.
	(c) Hussein, A. M. Heterocycl. Chem. 2012, 49, 446.
[7]	Gao, Q.; Sun, Z.; Xia, Q.; Li, R.; Wang, W.; Ma, S.; Chai, Y.; Wu, M.; Hu, W.; Brányi-Balogh, P. Á.; Keseru, G. M.; Han, X. Org. Lett. 2021, 23, 2664.
[8]	(a) Cherukupalli, S.; Karpoormath, R.; Chandrasekaran, B.; Hampannavar, G. A.; Thapliyal, N.; Palakollu, V. N. Eur. J. Med. Chem. 2017, 126, 298. doi: S0223-5234(16)30957-6 pmid: 27894044
	(b) Ren, J.; Ding, S. H.; Li, X. N.; Bi, R.; Zhao, Q. S. J. Org. Chem. 2021, 86, 12762. pmid: 27894044
[9]	(a) Hoang, G. L.; Streit, A. D.; Ellman, J. A. J. Org. Chem. 2018, 83, 15347. doi: 10.1021/acs.joc.8b02606 pmid: 29582661
	(b) Halskov, K. S.; Witten, M. R.; Hoang, G. L.; Mercado, B. Q.; Ellman, J. A. Org. Lett. 2018, 20, 2464. doi: 10.1021/acs.orglett.8b00816 pmid: 29582661
[10]	(a) Lian, F.; Xu, K.; Zeng, C. CCS Chem. 2023, 5, 1973.
	(b) Li, Q.; Zhang, H.; Liu, W. Chin. J. Org. Chem. 2023, 43, 3470 (in Chinese).
	(李奇阳, 张海燕, 刘文博, 有机化学, 2023, 43, 3470.)
	(c) Han, Q.; Xu, K.; Tian, F.; Huang, S.; Zeng, C. Chin. J. Org. Chem. 2022, 42, 1123 (in Chinese).
	(韩群, 徐坤, 田发宁, 黄胜阳, 曾程初, 有机化学, 2022, 42, 1123.)
[11]	In the presence of a cyanide ion, the Strecker-type side reaction would occur, see: (a) Feng, C. T.; Wei, H. J.; Li, J.; Peng, Y.; Xu, K. Adv. Synth. Catal. 2018, 360, 4726.
	(b) Qu, H. T.; Wu, Z. H.; Zhong, G. C.; Zhang, Y. C.; Feng, C. T.; Xu, K. Adv. Synth. Catal. 2023, 365, 871.
[12]	Cherukupalli, S.; Karpoormath, R.; Chandrasekaran, B.; Hampannavar, G. A.; Thapliyal, N.; Palakollu, V. N. Eur. J. Med. Chem. 2017, 126, 298. doi: S0223-5234(16)30957-6 pmid: 27894044
[13]	Yang, Q.; Yan, X. T.; Feng, C. T.; Chen, D. X.; Yan, Z. Z.; Xu, K. Org. Chem. Front. 2021, 8, 6384.
[14]	Selected examples on iodide-mediated transformations, see: (a) Sang, T.; Jia, F.; He, J.; Li, C.; Liu, Y.; Liu, P. Chin. J. Org. Chem. 2023, 43, 195 (in Chinese).
	(桑田, 贾帆, 何静, 李春天, 刘岩, 刘平, 有机化学, 2023, 43, 195.)
	(b) Yang, Z.; Cheng, Y.; Zhang, B.; Dong, Y.; Han, C.; Du, Y. Chin. J. Org. Chem. 2022, 42, 3456 (in Chinese).
	(杨治芳, 程乙夫, 张蓓蓓, 董韵怡, 韩驰, 杜云飞, 有机化学, 2022, 42, 3456.)
	(c) Chen, C.; Mo, D. Chin. J. Org. Chem. 2022, 42, 3012 (in Chinese).
	(陈春华, 莫冬亮, 有机化学, 2022, 42, 3012.) doi: 10.6023/cjoc202200052
	(d) Li, Q.; Wang, M.; Yu, W.; Chang, J.-B. Chin. J. Org. Chem. 2023, 43, 3966 (in Chinese).
	(李倩敏, 王漫漫, 于文全, 常俊标, 有机化学, 2023, 43, 3966.) doi: 10.6023/cjoc202305021
	(e) Wang, H.-Q.; Xu, K. Trans. Tianjin Univ. 2022, 28, 469.
	(f) Lian, F.; Xu, K.; Zeng, C. Chem. Rec. 2021, 21, 2290.
[15]	Other examples using thiocyanate salt as the “CN” source, see: (a) Zhang, G. Y.; Yu, J. T.; Hu, M. L.; Cheng, J. J. Org. Chem. 2013, 78, 2710.
	(b) Huang, Y. B.; Yu, Y.; Zhu, Z. Z.; Zhu, C. L.; Cen, J. H.; Li, X. W.; Wu, W. Q.; Jiang, H. F. J. Org. Chem. 2017, 82, 7621.
	(c) Guo, W.; Tan, W.; Zhao, M. M.; Zheng, L. Y.; Tao, K. L.; Chen, D. L.; Fan, X. L. J. Org. Chem. 2018, 83, 6580.
	(d) Wang, J. Y.; Sun, B.; Zhang, L.; Xu, T. W.; Xie, Y. Y.; Jin, C. Org. Chem. Front. 2020, 7, 113.
	(e) Yu, X.; Song, S. J.; Zhang, Z. H.; Liu, Y.; Zhang, M.; Zhu, W. J.; Duan, G. Y.; Zhu, W. J.; Zhang, P. F.; Ji, Y. F.; Xia, C. C. Adv. Synth. Catal. 2023, 365, 1640.
	(f) Grishin, S. S; Mulina, O. M.; Vil, V. A.; Terent'ev, A. O. Org. Chem. Front. 2024, 11, 327.
[16]	Liu, S.; Huang, W.; Wang, D.; Wei, P.; Shen, Q. Org. Chem. Front. 2016, 6, 2630.

Entry	[CN]	Oxidant	Solvent	Yield^b^,^c/%
1	TMSCN	I₂O₅	DMSO	36 (13)
2	NH₄SCN	I₂O₅	DMSO	52 (10)
3	NaSCN	I₂O₅	DMSO	42 (14)
4	KSCN	I₂O₅	DMSO	41 (12)
5	NH₄SCN	NaIO₄	DMSO	40 (19)
6	NH₄SCN	TBHP	DMSO	0 (0)
7	NH₄SCN	—	DMSO	0 (0)
8	TMSCN	—	DMSO	0 (0)
9^d	NH₄SCN	I₂O₅	EtOH	Trace (trace)
10^d	NH₄SCN	I₂O₅	DMF	Trace (trace)
11^d	NH₄SCN	I₂O₅	CH₃CN	31 (8)
12^d^,^e	NH₄SCN	I₂O₅	DMSO	79 (9)
13^d^,^e^,^f	NH₄SCN	I₂O₅	DMSO	76 (11)
14^d^,^e^,^g	NH₄SCN	I₂O₅	DMSO	62 (13)
15^d^,^e	—	I₂O₅	DMSO	26 (18)
16^d^,^e^,^h	—	I₂O₅	DMSO	24 (13)

Entry	[CN]	Oxidant	Solvent	Yield^b^,^c/%
1	TMSCN	I₂O₅	DMSO	36 (13)
2	NH₄SCN	I₂O₅	DMSO	52 (10)
3	NaSCN	I₂O₅	DMSO	42 (14)
4	KSCN	I₂O₅	DMSO	41 (12)
5	NH₄SCN	NaIO₄	DMSO	40 (19)
6	NH₄SCN	TBHP	DMSO	0 (0)
7	NH₄SCN	—	DMSO	0 (0)
8	TMSCN	—	DMSO	0 (0)
9^d	NH₄SCN	I₂O₅	EtOH	Trace (trace)
10^d	NH₄SCN	I₂O₅	DMF	Trace (trace)
11^d	NH₄SCN	I₂O₅	CH₃CN	31 (8)
12^d^,^e	NH₄SCN	I₂O₅	DMSO	79 (9)
13^d^,^e^,^f	NH₄SCN	I₂O₅	DMSO	76 (11)
14^d^,^e^,^g	NH₄SCN	I₂O₅	DMSO	62 (13)
15^d^,^e	—	I₂O₅	DMSO	26 (18)
16^d^,^e^,^h	—	I₂O₅	DMSO	24 (13)

硫氰酸铵促进的[3＋3]环化反应合成5-芳基吡唑并[1,5-a]嘧啶

NH₄SCN-Promoted Formal [3＋3] Annulation for the Synthesis of 5-Arylated Pyrazolo[1,5-a]pyrimidines

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 7

References 16

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Jiayan Du, Juntao Liu, Guixia Liu, Zheng Huang. Cobalt-Catalyzed Regio- and Stereoselective Isomerization of Terminal Alkenes to trans-2-Alkenes [J]. Chinese Journal of Organic Chemistry, 2024, 44(9): 2889-2897.
[2]	Jie Zhu, Sidan Tang, Xiumei Kan, Shizhu Fan, Pengfei Wang, Peijun Yang. Solvent-Controlled Sc(OTf)₃-Catalyzed Ring Opening Reaction of 2-(Hetero)aryl-N-sulfonylazetidines: Synthesis of Allylic Amines/1,3-Oxazinane Derivatives [J]. Chinese Journal of Organic Chemistry, 2024, 44(9): 2796-2809.
[3]	Lingyi Lu, Xiaodong Qiu. Recent Progress in Radical Involved Alkene Dialkylation [J]. Chinese Journal of Organic Chemistry, 2024, 44(6): 1701-1718.
[4]	Yunxin Xing, Denghong Yan, Shun Wen, Jie Bu, Kun Shen. Nickel-Catalyzed Reductive anti-Arylative Cyclization of 1,6-Enynes with Aryl Halides [J]. Chinese Journal of Organic Chemistry, 2024, 44(6): 1938-1948.
[5]	Xiaoyong Li, Danfeng Huang, Yuxiu Zhou, Xiaokang Liu, Kehu Wang, Junjiao Wang, Yulai Hu. [3+2] Cyclization of Difluoroacetohydrazonoyl Bromides with β-(N,N-Dimethylamino)enones/Enoates/Enamides [J]. Chinese Journal of Organic Chemistry, 2024, 44(4): 1226-1239.
[6]	Yatong Fu, Chaofan Sun, Dan Zhang, Chengguo Jin, Juyou Lu. Recent Progress in B—H Bond Functionalization of nido-Carboranes [J]. Chinese Journal of Organic Chemistry, 2024, 44(2): 438-447.
[7]	Jian Zhang, Wanjie Liang, Yi Yang, Fachao Yan, Hui Liu. Regiocontrollable Difunctionalization of N-Allenamines [J]. Chinese Journal of Organic Chemistry, 2024, 44(2): 335-348.
[8]	Xiaojing Hu, Feixiang Guo, Runqing Zhu, Bingqi Zhou, Tao Zhang, Lizhen Fang. Synthesis of p-Alkoxy Phenol and Its Application after Dearomatization [J]. Chinese Journal of Organic Chemistry, 2023, 43(6): 2239-2244.
[9]	Zhijun Ren, Weiwei Luo, Jun Zhou. Recent Progress in Silver-Mediated Tandem Cyclization of N-Arylacrylamides [J]. Chinese Journal of Organic Chemistry, 2023, 43(6): 2026-2039.
[10]	Jian Ji, Jinhua Liu, Cong Guan, Xuwen Chen, Yun Zhao, Shunying Liu. High Regioselective Synthesis of N²-Substituted-1,2,3-triazole via N-Sulfonyl-1,2,3-triazole Coupling with Alcohol Catalyzed by in-situ Generated Sulfonic Acid [J]. Chinese Journal of Organic Chemistry, 2023, 43(3): 1168-1176.
[11]	Wenting Wei, Zhuangzhuang Li, Wandi Li, Jiaqi Li, Xianying Shi. Green Method for Constructing Phthalides via Oxidative Coupling of Aromatic Acids and Acrylates in Neat Water and Air [J]. Chinese Journal of Organic Chemistry, 2023, 43(3): 1177-1186.
[12]	Ning Liu, Xiaodan Cuan, Hui Li, Xiyan Duan. Progress in the Study of α-Functionalization of Enaminone [J]. Chinese Journal of Organic Chemistry, 2023, 43(2): 602-621.
[13]	Yu Zhao, Yurong Duan, Shihui Shi, Yubin Bai, Liangzhu Huang, Xiaojun Yang, Yantu Zhang, Bin Feng, Jianbo Zhang, Qiuyu Zhang. Recent Advances of Hypervalent Iodine(III) Reagents upon Visible Light Irradiation [J]. Chinese Journal of Organic Chemistry, 2023, 43(12): 4106-4140.
[14]	Duoduo Xiao, Jiantao Zhang, Peng Zhou, Weibing Liu. Metal-Free α-C(sp³)—H Methylenation of Aryl Ketones to Form γ-Keto Sulfoxides with Dimethyl Sulfoxide [J]. Chinese Journal of Organic Chemistry, 2023, 43(11): 3900-3906.
[15]	Huaiyuan Zhang, Nuo Xu, Rongping Tang, Xingli Shi. Recent Advances in Asymmetric Dearomatization Reactions Induced by Chiral Hypervalent Iodine Reagents [J]. Chinese Journal of Organic Chemistry, 2023, 43(11): 3784-3805.