N-Heterocyclic Carbene-Catalyzed [4＋2] Cycloaddition of Salicylaldehydes with Pyrazole-4,5-diones for the Synthesis of Spiroketal-Pyrazolones

doi:10.6023/cjoc202406005

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (1): 267-275.DOI: 10.6023/cjoc202406005 Previous Articles Next Articles

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氮杂环卡宾(NHC)催化水杨醛与吡唑啉酮-4,5-二酮的[4＋2]环加成反应高效构建螺缩酮-吡唑啉酮化合物

王晓梅, 刘岩, 李师伍^*(), 赵志飞^*()

石河子大学化学化工学院化工绿色过程省部共建国家重点实验室培育基地新疆石河子 832000

收稿日期:2024-06-04 修回日期:2024-07-10 发布日期:2024-08-23
基金资助:
石河子大学(2022ZK003); 石河子大学(RCZK202001); 新疆维吾尔自治区“天池英才”引进(CZ002737)

N-Heterocyclic Carbene-Catalyzed [4＋2] Cycloaddition of Salicylaldehydes with Pyrazole-4,5-diones for the Synthesis of Spiroketal-Pyrazolones

Xiaomei Wang, Yan Liu, Shiwu Li(), Zhifei Zhao()

State Key Laboratory Incubation Base for Green Processing of Chemical Engineering, School of Chemistry and Chemical Engineering, Shihezi University, Shihezi, Xinjiang 832000

Received:2024-06-04 Revised:2024-07-10 Published:2024-08-23
Contact: *E-mail: zhaozf@shzu.edu.cn; lishiwu@shzu.edu.cn
Supported by:
Shihezi University(2022ZK003); Shihezi University(RCZK202001); Tianchi Talent Project of Xinjiang Uygur Autonomous Region(CZ002737)

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Abstract

The first efficiently N-heterocyclic carbene-catalyzed [4＋2] cycloaddition of salicylaldehydes and pyrazole-4,5- diones to directly synthesis of spiro-ketal-pyrazolones bearing both oxygens of the ketal unit in the same ring was disclosed. This reaction was qualified with broad substrate scope, achieving moderate to excellent yield (up to 98%). This method has mild reaction conditions and simple operation, providing a new attractive strategy for the practical syntheses of multi- functionalized spiroketals including pyrazolone structures with mild reaction condition and operational simplicity. Furthermore, the gram scale and derivative transformations have also been achieved.

Key words: N-heterocyclic carbene, cycloaddition, salicylaldehyde, pyrazole-4,5-dione, spiro-ketal-pyrazolone

Cite this article

Xiaomei Wang, Yan Liu, Shiwu Li, Zhifei Zhao. N-Heterocyclic Carbene-Catalyzed [4＋2] Cycloaddition of Salicylaldehydes with Pyrazole-4,5-diones for the Synthesis of Spiroketal-Pyrazolones[J]. Chinese Journal of Organic Chemistry, 2025, 45(1): 267-275.

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References 11

[1]	For reviews on spirocyclic compounds, see: (a) Carreira, E. M.; Fessard, T. C. Chem. Rev. 2014, 114, 8257.
	(b) Rios, R. Chem. Soc. Rev. 2012, 41, 1060.
	(c) Kotha, S.; Panguluri, N. R.; Ali, R. Eur. J. Org. Chem. 2017, 2017, 5316.
	(d) Sorensen, E. J.; Davies, H. M. L. Chem. Soc. Rev. 2009, 38, 2969.
	(e) Singh, G. S.; Desta, Z. Y. Chem. Rev. 2012, 112, 6104.
	(f) Galliford, C.; Scheidt, V. K. A. Angew. Chem., Int. Ed. 2007, 46, 8748.
	(g) Cao, Z. Y.; Zhou, J. Org. Chem. Front. 2015, 2, 849.
[2]	For selected examples on spiroketal see: (a) Aho, J. E.; Pihko, P. M.; Rissa, T. K. Chem. Rev. 2005, 105, 4406.
	(b) Liu, L.; Li, Y.; Li, L.; Cao, Y.; Guo, L. D.; Liu, G.; Che, Y. S. J. Org. Chem. 2013, 78, 2992.
	(c) Zhang, S. Y.; Tu, Y. Q. Nat. Prod. Rep. 2018, 35, 75.
	(d) Liu, L.; Han, Y.; Xiao, J. H.; Li, L.; Guo, L. D.; Jiang, X. J.; Kong, L. Y.; Che, Y. S. J. Nat. Prod. 2016, 79, 2616.
	(e) Rizzacasa, M. A.; Pollex, A. Org. Biomol. Chem. 2009, 7, 1053.
	(f) Sahoo, S. R.; Sarkar, D. Tetrahedron Lett. 2020, 61, 151646.
[3]	Perron, F.; Albizati, K. F. Chem. Rev. 1989, 89, 1617.
[4]	(a) Limbadri, S.; Luo, X. L.; Lin, X. P.; Wang, J. F.; Yang, B.; Zhou, X. F.; Liu, Y. H. Org. Biomol. Chem. 2019, 17, 2182.
	(b) Aho, J. E.; Pihko, P. M.; Rissa, T. K. Chem. Rev. 2005, 105, 4406.
	(c) Yan, H.; Zhang, M.; Li, L.; Hu, T.; Yang, W. L. Chin. J. Org. Chem. 2022, 42, 3640 (in Chinese).
	(闫辉, 张曼, 李琳, 胡腾, 杨武林, 有机化学, 2022, 42, 3640.)
[5]	For selected examples on spiropyrazolone see: (a) Bondock, S.; Rabie, R.; Etman, H. A.; Fadda, A. A. Eur. J. Med. Chem. 2008, 43, 2122.
	(b) Zea, A.; Alba, A.-N. R.; Mazzanti, A.; Moyano, A.; Rios, R. Org. Biomol. Chem. 2011, 9, 6519.
	(c) Zheng, J.; Wang, S.-B.; Zheng, C.; You, S.-L. Angew. Chem., Int. Ed. 2017, 56, 4540.
	(d) Zhang, J.-X.; Li, N.-K.; Liu, Z.-M.; Huang, X.-F.; Geng, Z.-C.; Wang, X.-W. Adv. Synth. Catal. 2013, 355, 797.
	(e) Luo, W. J.; Shao, B. X.; Li, J. Y.; Xiao, X.; Song, D. G.; Ling, F.; Zhong, W. H. Org. Chem. Front. 2020, 7, 1016.
	(f) Warghude, P. K.; Bhowmick, A.; Bhat, R. G. Tetrahedron Lett. 2022, 97, 153791.
	(g) Warghude, P. K.; Sabale, A. S.; Bhat, R. G. Org. Biomol. Chem. 2020, 18, 1794.
	(h) Liu, X. L.; Zuo, X.; Wang, J. X.; Chang, S. Q.; Wei, Q. D.; Zhou, Y. Org. Chem. Front. 2019, 6, 1485.
	(i) Wang, C.; Wen, D. W.; Chen, H.; Deng, Y. B.; Liu, X. T.; Liu, X.; Wang, L.; Gao, F. Y.; Guo, Y. F.; Sun, M. M.; Wang, K. R.; Yan, W. J. Org. Biomol. Chem. 2019, 17, 5514.
	(j) Lin, Y.; Zhao, B. L.; Du, D. M. J. Org. Chem. 2019, 84, 10209.
	(k) Bao, X. Z.; Wei, S. Q.; Qian, X. K.; Qu, J. P.; Wang, B. M.; Zou, L. W.; Ge, G. B. Org. Lett. 2018, 20, 3394.
	(l) Li, J. H.; Feng, T. F.; Du, D. M. J. Org. Chem. 2015, 80, 11369.
	(m) Cui, B. D.; Li, S. W.; Zuo, J.; Wu, Z. J.; Zhang, X. M.; Yuan, W. C. Tetrahedron 2014, 70, 1895.
	(n) Chen, Q.; Liang, J. Y.; Wang, S. L.; Wang, D.; Wang, R. Chem. Commun. 2013, 49, 1657.
[6]	(a) Das, D.; Banerjee, R.; Mitra, A. J. Chem. Pharm. Res. 2014, 6, 108.
	(b) Chande, M. S.; Barve, P. A. J. Heterocycl. Chem. 2007, 44, 49.
[7]	(a) Talevi, A. Front. Pharmacol. 2015, 6, 205.
	(b) Pagliero, R. J.; Kaiser, M.; Brun, R.; Nieto, M. J.; Mazzieri, M. R. Bioorg. Med. Chem. Lett. 2017, 27, 3945.
	(c) Klahn, P.; Brönstrup, M. Nat. Prod. Rep. 2017, 34, 832.
	(d) Fu, R. G.; Sun, Y.; Sheng, W. B.; Liao, D. F. Eur. J. Med. Chem. 2017, 136, 195.
	(e) Leng, H. J.; Li, Q. Z.; Zeng, R.; Dai, Q. S.; Zhu, H. P.; Liu, Y.; Huang, W.; Han, B.; Li, J. L. Adv. Synth. Catal. 2018, 360, 229.
	(f) Mondal, S.; Mukherjee, S.; Yetra, S. R.; Gonnade, R. G.; Biju, A. T. Org. Lett. 2017, 19, 4367.
[8]	Liu, Y.; Zhang, X. R.; Zeng, Y.; Dai, Q. S.; Leng, H. J.; Gou, X. J.; Li, J. L. Molecules 2017, 22, 1882.
[9]	Chen, X.; Wang, H.; Doitomi, K.; Zheng, C. Y. O.; Liu, P. W.; Guo, H.; Yang, S.; Song, B. A.; Hirao, H.; Chi, Y. R. Nat. Commun. 2017, 8, 15598.
[10]	(a) Han, Y. F.; Gao, Z. H.; Zhang, C. L.; Ye, S. Org. Lett. 2020, 22, 8396.
	(b) Lee, A.; Zhu, J. L.; Feoktistova, T.; Brueckner, A. C.; Cheong, P. H.-Y.; Scheidt, K. A. Angew. Chem., Int. Ed. 2019, 58, 5941.
	(c) Li, Y. Y.; Li, S.; Fan, T.; Zhang, Z. J.; Song, J.; Gong, L. Z. ACS Catal. 2021, 11, 14388.
[11]	(a) Phelan, J. P.; Ellman, J. A. Adv. Synth. Catal. 2016, 358, 1713.
	(b) Kaya, U.; Chauhan, P.; Mahajan, S.; Deckers, K.; Valkonen, A.; Rissanen, K.; Enders, D. Angew. Chem. 2017, 129, 15560.

Entry	Catalyst	Base (mol%)	Solvent	T/℃	Yield^b/%
1	A1	Et₃N (150)	THF	25	49
2	A2	Et₃N (150)	THF	25	46
3	A3	Et₃N (150)	THF	25	73
4	A4	Et₃N (150)	THF	25	16
5	A5	Et₃N (150)	THF	25	21
6	A6	Et₃N (150)	THF	25	Trace
7	A7	Et₃N (150)	THF	25	Trace
8	A3	Et₃N (50)	THF	25	74
9	A3	DBU (50)	THF	25	68
10	A3	Cs₂CO₃ (50)	THF	25	71
11	A3	NaOH (50)	THF	25	69
12	A3	^tBuOK (50)	THF	25	79
13	A3	KOH (50)	THF	25	82
14	A3	KOH (50)	DCM	25	65
15	A3	KOH (50)	EtOAc	25	63
16	A3	KOH (50)	THF	30	54
17	A3	KOH (50)	THF	－10	66

Entry	Catalyst	Base (mol%)	Solvent	T/℃	Yield^b/%
1	A1	Et₃N (150)	THF	25	49
2	A2	Et₃N (150)	THF	25	46
3	A3	Et₃N (150)	THF	25	73
4	A4	Et₃N (150)	THF	25	16
5	A5	Et₃N (150)	THF	25	21
6	A6	Et₃N (150)	THF	25	Trace
7	A7	Et₃N (150)	THF	25	Trace
8	A3	Et₃N (50)	THF	25	74
9	A3	DBU (50)	THF	25	68
10	A3	Cs₂CO₃ (50)	THF	25	71
11	A3	NaOH (50)	THF	25	69
12	A3	^tBuOK (50)	THF	25	79
13	A3	KOH (50)	THF	25	82
14	A3	KOH (50)	DCM	25	65
15	A3	KOH (50)	EtOAc	25	63
16	A3	KOH (50)	THF	30	54
17	A3	KOH (50)	THF	－10	66

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氮杂环卡宾(NHC)催化水杨醛与吡唑啉酮-4,5-二酮的[4＋2]环加成反应高效构建螺缩酮-吡唑啉酮化合物

N-Heterocyclic Carbene-Catalyzed [4＋2] Cycloaddition of Salicylaldehydes with Pyrazole-4,5-diones for the Synthesis of Spiroketal-Pyrazolones

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