Organic Base-Promoted [2+3] Annulation of Arylglyoxal Monohydrates with Allyl Phosphonium Salts: Efficient Syntheses of Cyclopentenones

doi:10.6023/cjoc202502010

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (9): 3420-3428.DOI: 10.6023/cjoc202502010 Previous Articles Next Articles

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有机碱促进的芳基乙二醛一水合物与烯丙基鏻盐的[2+3]环加成反应: 高效合成环戊烯酮类化合物

张森^†, 江凌云^†, 辛雨, 黄年玉^*(), 王能中^*()

三峡大学生物与制药学院天然产物研究与利用湖北省重点实验室湖北宜昌 443002

收稿日期:2025-02-13 修回日期:2025-04-22 发布日期:2025-05-15
作者简介:
† 共同第一作者
基金资助:
高等学校学科创新引智计划(111 Project); 高等学校学科创新引智计划(D20015); 宜昌市自然科学研究项目(A23-2-002); 天然产物研究与利用湖北省重点实验室(三峡大学)开放基金(2024NPRD04)

Organic Base-Promoted [2+3] Annulation of Arylglyoxal Monohydrates with Allyl Phosphonium Salts: Efficient Syntheses of Cyclopentenones

Sen Zhang, Lingyun Jiang, Yu Xin, Nianyu Huang^*(), Nengzhong Wang^*()

Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang, Hubei 443002

Received:2025-02-13 Revised:2025-04-22 Published:2025-05-15
Contact: *E-mail: huangny@ctgu.edu.cn; wangnz@ctgu.edu.cn
About author:
† These authors contributed equally to this work
Supported by:
Programme of Introducing Talents of Discipline to Universities(111 Project); Programme of Introducing Talents of Discipline to Universities(D20015); Natural Science Research Project of Yichang City(A23-2-002); Opening Funding of Hubei Key Laboratory of Natural Products Research and Development, China Three Gorges University(2024NPRD04)

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Abstract

Cyclopentenone compounds are widely present in natural products and biologically active molecules, and act as very powerful synthons for the synthesis of a variety of bioactive target molecules. Therefore, it is of great research significance and application value to develop their synthetic methods. This article reports a novel method for the efficient synthesis of cyclopentenones by organic base-promoted [2+3] annulation reaction of arylglyoxal monohydrates with allyl phosphonium salts. This method displays metal-free, good chemoselectivity, mild reaction conditions, broad substrate scope, and short reaction time. The practical application of this method is demonstrated by the gram-scale synthesis and further transformation reactions.

Key words: organic base, [2+3] annulation, arylglyoxal monohydrates, allyl phosphonium salts, cyclopentenones

Cite this article

Sen Zhang, Lingyun Jiang, Yu Xin, Nianyu Huang, Nengzhong Wang. Organic Base-Promoted [2+3] Annulation of Arylglyoxal Monohydrates with Allyl Phosphonium Salts: Efficient Syntheses of Cyclopentenones[J]. Chinese Journal of Organic Chemistry, 2025, 45(9): 3420-3428.

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Fig. & Tab. 9

Figure 1. Representative natural products

Scheme 1. The reactions of allyl phosphonium salts

Entry	Base	Time/min	Solvent	Yield^b/%
1 2 3 4 5 6 7 8 9 10 11 12	K₂CO₃ NaOH NaO^tBu DMAP DABCO DABCO DABCO DABCO DABCO DABCO DABCO DABCO	10 10 10 10 10 30 60 10 10 10 10 10	MeCN MeCN MeCN MeCN MeCN MeCN MeCN Toluene THF Acetone DCM MeOH	N.D. N.D. N.D. 28 42 37 31 44 47 67 78 54

Table 1. Optimization of reaction condition

Scheme 2. Substrate scope of allyl phosphonium salts

Scheme 3. Substrate scope of arylglyoxal monohydrates

Scheme 4. Gram-scale reaction

Scheme 5. Further transformations of 3a

Scheme 6. Mechanistic studies

Scheme 7. Proposed reaction mechanism

References 15

[1]	(a) Kunitada, T.; Omatsu, R.; Tanaka, N.; Imai, N.; Inokuchi, T.; Nokami, J. Tetrahedron Lett. 2010, 51, 5525.
	(b) Pohmakotr, M.; Kambutong, S.; Tuchinda, P.; Kuhakarn, C. Tetrahedron 2008, 64, 6315.
	(c) Matsuo, N.; Sugisaka, Y.; Aoyama, S.; Ihara, M.; Shinoyama, H.; Hosokawa, M.; Kamakura, Y.; Tanaka, D.; Tanabe, Y.; Matsuda, K. J. Med. Chem. 2023, 66, 7959.
	(d) Kashanna, J.; Jangili, P.; Kumar, R.-A.; Rao, R. B.-R. Tetrahedron Lett. 2013, 54, 1634.
	(e) Xu, G.; Hou, A.-J.; Zheng, Y.-T.; Zhao, Y.; Li, X.-L.; Peng, L.-Y.; Zhao, Q.-S. Org. Lett. 2007, 9, 291.
	(f) Hao, Z.-Y.; Liang, D.; Luo, H.; Liu, Y.-F.; Ni, G.; Zhang, Q.-J.; Li, L.; Si, Y.-K.; Sun, H.; Chen, R.-Y.; Yu, D.-Q. J. Nat. Prod. 2012, 75, 1083.
[2]	(a) Simeonov, S. P.; Nunes, J. P. M.; Guerra, K.; Kurteva, V. B.; Afonso, C. A. M. Chem. Rev. 2016, 116, 5744. doi: 10.1021/cr500504w pmid: 27101336
	(b) Jose, J.; Mathew, T. V. Tetrahedron 2024, 150, 133747. pmid: 27101336
[3]	(a) Wang, H. Zhang, H.; Yang, B.; He, H.; Gao, S. J. Am. Chem. Soc. 2023, 145, 16988.
	(b) Xue, Y.; Hou, S.-H.; Zhang, X.; Zhang, F.-M.; Zhang, X.-M.; Tu, Y.-Q. J. Am. Chem. Soc. 2024, 146, 25445.
	(c) Botlik, B. B.; Weber, M.; Ruepp, F.; Kawanaka, K.; Finkelstein, P.; Morandi, B. Angew. Chem., Int. Ed. 2024, 63, e202408230.
[4]	(a) Li, M.; Meng, B.; Lan, W.; Fu, B. Chin. J. Org. Chem. 2024, 44, 195. (in Chinese)
	(李梦竹, 孟博莹, 兰文捷, 傅滨, 有机化学, 2024, 44, 195.) doi: 10.6023/cjoc202307019
[5]	(a) Li, X.; Huang, D.; Zhou, Y.; Liu, X.; Wang, K.; Wang, J.; Hu, Y. Chin. J. Org. Chem. 2024, 44, 1226. (in Chinese)
	(李晓勇, 黄丹凤, 周玉秀, 刘小康, 王克虎, 王君娇, 胡雨来, 有机化学, 2024, 44, 1226.) doi: 10.6023/cjoc202311001
	(b) Xu, M.; You, M.; Su, Y.; Lu, B. R.; Liu, L.; Lv, X.; Wang, S.; Mao, H.; Zhou, L. Org. Chem. Front. 2023, 10, 1521.
	(c) Wu, H.; Wang, J.; Jing, H.; Zhang, Z.; Ou, W.; Su, C. Org. Lett. 2024, 26, 5415.
	(d) Wang, H.; Niu, W.; Wei, M.; Xiao, Y.; Lin, Y.-W. Org. Lett. 2025, 27, 2721.
	(e) Zhang, S.; Gan, M.; Zhang, F.; Zhou, L.; Li, W. Org. Lett. 2025, 27, 3013.
[6]	(a) Wang, N.; Lang, Y.; Wang, J.; Wu, Z.; Lu, Y. Org. Lett. 2022, 24, 3712.
	(b) Chen, Z.; Xiong, D.; Wang, N.; Zhang, Y.; Yao, H.; Zhang, J.; Huang, N.; Zou, K. Org. Chem. Front. 2024, 11, 2762.
	(c) Li, S.; Xu, D.; Yao, H.; Tan, M.; Li, X.; Liu, M.; Wang, L.; Huang, N.; Wang, N. Chem. Commun. 2024, 60, 6773.
	(d) Li, B.; Hu, X.; Yao, H.; Li, Y.; Xu, D.; Huang, N.; Wang, N. Org. Lett. 2024, 26, 7576.
	(e) Tan, M.; Zheng, Y.; Zhang, S.; Yao, H.; Yan, X.; Zhao, X.; Liu, M.; Huang, N.; Wang, N. Org. Lett. 2024, 26, 9203.
	(f) Li, Y.; Hu, X.; Li, B.; Zhang, S.; Yao, H.; Xiao, X.; Huang, N.; Wang, N. Org. Lett. 2024, 26, 10651.
	(g) Chen, G.; Nie, G.; Li, L.; Fu, J.; Yao, H.; Huang, N.; Wang, N. Org. Chem. Front. 2025, 12, 2212.
	(h) Zhang, Y.; Chen, J.; Yao, H.; Wang, Y.; Liu, H.; Wang, L. Huang, N.; Wang, N. Chin. J. Chem. 2025, 43, 995.
[7]	(a) Ye, L.-W.; Han, X.; Sun, X.-L.; Tang, Y. Tetrahedron 2008, 64, 8149.
	(b) Ye, L.-W.; Wang, S.-B.; Wang, Q.-G.; Sun, X.-L.; Tang, Y.; Zhou, Y.-G. Chem. Commun. 2009, 3092.
	(c) Wang, Q.; Sun, X.; Zheng, J.; Tang, Y. Chin. J. Chem. 2010, 28, 1618.
	(d) Shu, Z.-C.; Zhu, J.-B.; Liao, S.; Sun, X.-L.; Tang, Y. Tetrahedron 2013, 69, 284.
	(e) Wang, P.; Liao, S.; Zhu, J.-B.; Tang, Y. Chem. Commun. 2014, 50, 808.
	(f) Liu, S.; Chen, W.; Luo, J.; Yu, Y. Chem. Commun. 2014, 50, 8539.
	(g) Li, K.; Yu, A; Meng, X. Org. Lett. 2018, 20, 1106.
	(h) Li, K.; Wang, L.; Yu, A.; Zhu, L.; Gu, Y.; Zhang, L.; Meng, X. Chem.-Eur. J. 2019, 25, 9665.
[8]	(a) Eftekhari-Sis, B.; Zirak, M.; Akbari, A. Chem. Rev. 2013, 113, 2958. doi: 10.1021/cr300176g pmid: 23347156
	(b) Chaudhary, A. Curr. Org. Chem. 2019, 23, 1945. doi: 10.2174/1385272823666191019110010 pmid: 23347156
	(c) He, L.; Lv, H.; Zhang, Y.-R.; Ye, S. J. Org. Chem. 2008, 73, 8101. pmid: 23347156
	(d) Fan, W.; Ye, Q.; Xu, H.-W.; Jiang, B.; Wang, S.-L.; Tu, S.-J. Org. Lett. 2013, 15, 2258. pmid: 23347156
	(e) Feng, X.; Wang, Q.; Lin, W.; Dou, G.-L.; Huang, Z.-B.; Shi, D.-Q. Org. Lett. 2013, 15, 2542. pmid: 23347156
	(f) Shu, W.-M.; Zheng, K.-L.; Ma, J.-R.; Sun, H.-Y.; Wang, M.; Wu, A.-X. Org. Lett. 2015, 17, 1914. pmid: 23347156
	(g) Li, X.-Y.; Yuan, W.-Q.; Tang, S.; Huang, Y.-W.; Xue, J.-H.; Fu, L.-N.; Guo, Q.-X. Org. Lett. 2017, 19, 1120. pmid: 23347156
	(h) Li, K.; Chen, L.; Fan, Y.-X.; Wei, Y.; Yan, S.-J. J. Org. Chem. 2019, 84, 11971. pmid: 23347156
[9]	Wang, Y.; Li, Y.; Lian, M.; Zhang, J.; Liu, Z.; Tang, X.; Yin, H.; Meng, Q. Org. Biomol. Chem. 2019, 17, 573.
[10]	(a) Lu, M.; Zhu, D.; Lu, Y.; Zeng, X.; Tan, B.; Xu, Z.; Zhong, G. J. Am. Chem. Soc. 2009, 131, 4562.
	(b) Isaka, N.; Tamiya, M.; Hasegawa, A.; Ishiguro, M. Eur. J. Org. Chem. 2012, 665.
	(c) Wang, Y.; Lu, R.; Yao, J.; Li, H. Angew. Chem., Int. Ed. 2021, 60, 6631.
[11]	(a) Li, H.; Wang, K.; Zhao, W.; Li, X.; Fu, Y.; Do, H.; An, J.; Hu, Z. Org. Lett. 2024, 26, 9120.
	(b) Li, L.; Chen, X.; Pei, C.; Li, J.; Zou, D.; Wu, Y.; Wu, Y. Chin. J. Org. Chem. 2021, 41, 2319. (in Chinese)
	(李琳琳, 陈晓雨, 裴聪聪, 李敬亚, 邹大鹏, 吴养洁, 吴豫生, 有机化学, 2021, 41, 2319.) doi: 10.6023/cjoc202012020
[12]	(a) Wu, J.; Jiang, X.; Xu, J.; Dai, W.-M. Tetrahedron 2011, 67, 179.
	(b) Xun, W.; Xu, B.; Chen, B.; Meng, S.; Chan, A. S. C.; Qiu, F. G.; Zhao, J. Org. Lett. 2018, 20, 590.
	(c) Yu, X.; Huang, N.; Huo, Y.; Li, X.; Liu, Y.; Maruoka, K.; Chen, Q. Org. Lett. 2024, 26, 565.
	(d) Wang, M.; He, Y.-Q.; Zhu, Y.; Song, Z.-B.; Wang, X.-Y.; Huang, H.-Y.; Cao, B.-P.; Tian, W.-F.; Xiao, Q. Org. Chem. Front. 2021, 8, 5934.
[13]	(a) Martinez-Erro, S.; Sanz-Marco, A.; Gomez, A. B.; Vazquez- Romero, A.; Ahlquist, M. S. G.; Martín-Matute, B. J. Am. Chem. Soc. 2016, 138, 13408. doi: 10.1021/jacs.6b08350 pmid: 33724037
	(b) Mondal, K.; Mondal, B.; Pan, S. C. J. Org. Chem. 2016, 81, 4835. pmid: 33724037
	(c) Zhang, L.; Wang, B.; Zhao, Y.; Pu, M.; Liu, S.; Lei, M. J. Phys. Chem. A 2021, 125, 2316. doi: 10.1021/acs.jpca.1c00404 pmid: 33724037
	(d) Sai, M. Eur. J. Org. Chem. 2022, e202200052. pmid: 33724037
[14]	(a) Cai, Q.; Zhuang, S.; Yang, M.; Peng, N.; Liu, Y.; Wu, A. Tetrahedron, 2019, 75, 130756.
	(b) Zhan, Z.; Zhang, G.; Cheng, X.; Lv, G.; Zheng, Y.; Hai, L.; Wu, Y. Chin. J. Org. Chem. 2015, 35, 2559. (in Chinese)
	(展震, 张国尧, 程旭, 吕光辉, 郑阳, 海俐, 吴勇, 有机化学, 2015, 35, 2559.)
[15]	Mathieson, J. E.; Crawford, J. J.; Schmidtmann, M.; Marquez, R. Org. Biomol. Chem. 2009, 7, 2170. doi: 10.1039/b901797f pmid: 19421456

有机碱促进的芳基乙二醛一水合物与烯丙基鏻盐的[2+3]环加成反应: 高效合成环戊烯酮类化合物

Organic Base-Promoted [2+3] Annulation of Arylglyoxal Monohydrates with Allyl Phosphonium Salts: Efficient Syntheses of Cyclopentenones

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