SIOC 中文
CJOG
Adv search

Chinese Journal of Organic Chemistry >

0 202604009

DOI: https://doi.org/10.6023/cjoc202604009

ARTICLE

Phosphine-Catalyzed [3+2] and [4+2] Annulations of Amino(Hydroxyl)-Substituted α,β-Unsaturated Esters(Ketones) with Iso(thio)cyanates

  • 胡燚 ,
  • 蔡逸飞 ,
  • 高浩杰 ,
  • 姜磬歌 ,
  • 刘明国 ,
  • 王能中 ,
  • 黄年玉
Expand
  • Key Laboratory of Natural Products Research and Development, College of Biological and Pharmaceutical Sciences, China Three Gorges University, Yichang Hubei 443002
†These authors contributed equally to this work.

Received date: 2026-06-16

  Revised date: 2026-07-14

  Online published: 2026-08-24

Supported by

111 Project (No. D20015), the Hubei Provincial Natural Science Foundation Joint Fund for Innovation and Development Project of Yichang (2025AFD262), and the Hubei Provincial Central Government Guided Local Science and Technology Development Project (2024BSB016).

Fold

Abstract

Five- and six-membered saturated polyheterocyclic compounds are widely found in natural products and pharmaceuticals with excellent biological activities. These scaffolds have attracted significant attention in organic synthesis. However, constructing these scaffolds typically requires different approaches, resulting in low synthetic efficiency. This paper reports a novel method for the efficient divergent synthesis of imidazolidinones, oxazolidinones, imidazolidinethiones, oxazolidinethiones tetrahydropyrimidinones, and oxazinanones via phosphine-catalyzed [3+2] and [4+2] annulations of amino (hydroxyl)-substituted α,β-unsaturated esters (ketones) with iso(thio)cyanates. This method offers advantages such as simple operation, broad substrate scope, and 100% atom economy. Gram-scale synthesis and further transformations demonstrate its good application potential.

Key words： phosphine catalysis; annulation; imidazolidinone; tetrahydropyrimidinone; oxazinanone

Cite this article

胡燚 , 蔡逸飞 , 高浩杰 , 姜磬歌 , 刘明国 , 王能中 , 黄年玉 . Phosphine-Catalyzed [3+2] and [4+2] Annulations of Amino(Hydroxyl)-Substituted α,β-Unsaturated Esters(Ketones) with Iso(thio)cyanates[J]. Chinese Journal of Organic Chemistry, 0 : 202604009 . DOI: 10.6023/cjoc202604009

References

[1] (a) Spencer C. M.; Gunasekara N. S.; Hills C.; Drugs1999, 58, 347.
(b) Fortin S.; Xavier, C -M.; Turcotte, V; Lauvaux C.; Lacroix J.; Cite M.-F.; Gobeil S.; Rene, C.-G. J. Med. Chem.2017, 60, 4963.
(c) Rokach J.; Hamel P.; Hunter N. R.; Reader G.; Rooney C. S.; Anderson P. S.; Jr E. J. C.; Mandel L. R. J. Med. Chem.1979, 22, 237.
(d) Astwood E. B.; Greer M. A.; Ettlinger, M. G. J. Bio. Chem.1949, 181, 121.
(e) Alizadeh A.; Salouti M.; Alizadeh H.; Kazemizadeh A. R.; Safari A.-R.; Mahmazi S. IET Nanobiotechnol.2017, 11, 942.
(f) Boegesoe K. P.; Arnt J.; Boeck V.; Christensen A. V.; Hyttel J.; Jensen, K. G. J. Med. Chem.1988, 31, 2247.
[2] (a) Zhao, Q.-Y.; Lian, Z.; Wei, Y.; Shi, M.; Chem. Commun. 2012, 48, 1724.
(b) Alvarez, A. C. C.; Bouzriba, C.; Moreau, E.; Auzeloux, P.; Besse, S.; Ouellette, V. Khosroshahi, M. Z.; Cote, M. F.; Pilote, S.; Miot-Noirault, E. Chezal, J. M.; Simard, C.; C-Gaudreault, R. C.; Fortin, S.; J. Med. Chem. 2023, 66, 2477.
(c) Kupchan, S. M.; ,Komoda, Y.; Court, W. A.; Thomas, G. J.; Smith, R. M.; Karim, A.; Gilmore, C. J.; Haltiwanger, R. C.; Bryan, R.; J. Am. Chem. Soc. 1972, 94, 1354.
(d) Yokota, T.; Tomita, H. Mori, Y.; Kudo, T.; Hiraga, H.; Suto, N.; Higuma, T.; Abe, N.; Hanada, H.; Osanai, T.; Okumura, K.; J. Cardiovasc. Pharmacol. 2014, 63, 528.
(e) Kawamura, M.; Konishi, N.; Hiroe, K.; Shofuda, K.; Imaeda, Y.; Fujimoto, T.; Kubo, K.; J. Cardiovasc. Pharmacol. 2010, 56, 156.
(f) Gagne-Boulet, M.; Fortin, S.; Lacroix, J.; Lefebvre, C. A.; Cote, M. F.; Gaudreault, R. C.; Eur. J. Med. Chem. 2015, 100, 34.
(g) Lam P. Y.; Jadhav P. K.; Eyermann C. J.; Hodge C. N.; Ru Y.; Bacheler L. T.; Meek J. L.; Otto M. J.; Rayner M. M.; Wong Y. N.; Science1994, 263, 380.
[3] (a) Li C.-L.; Yu, Z.-X. Chin. J. Org. Chem.2024, 44, 1045. (in Chinese)
(李晨龙余志祥, 有机化学, 2024, 44, 1405.)
(b) Zhang J.; Xu M.; Gu M.; Ma H.; Cai, Q. Acta Chim. Sinica2025, 83, 667. (in Chinese)
(张豪杰, 徐明金, 古满珍, 马浩文, 蔡倩, 化学学报, 2025, 83, 667.)
(c) Zhu Z.; Ye L.; Wu Y.; Guo Z.; Shi, F. Acta Chim. Sinica2025, 83, 1465. (in Chinese)
(朱子琦, 叶乐华, 吴怡, 郭梓圻, 石枫, 化学学报, 2025, 83, 1465.)
[4] (a) Ren H.; Ma M.; Huang, Y. Chin. J. Org. Chem.2022, 42, 3129. (in Chinese)
(任红霞, 马萌萌, 黄有, 有机化学, 2022, 42, 3129.)
(b) Tan W.; Zhang J.-Y.; Gao C.-H.; Shi, F. Sci. China Chem.2023, 66, 966.
(c) Chen X.; Li P. Chem. Rec.2023, 23, e202300152.
(d) Otevrel, J.; Eugui, M.; Ričko, S.; Jørgensen, K. A.; Nat. Synth. 2023, 2, 1142.
(e) Pan X.; Huang, Y. Chin. J. Org. Chem.2024, 44, 3609. (in Chinese)
(潘旭玲, 黄有, 有机化学, 2024, 44, 3609.)
(f) Zhu, Z.-Q.; Li, T.-Z.; Liu, S.-J.; Shi, F.; Org. Chem. Front. 2024, 11, 5573.
[5] (a) Wang, N.; Lang, Y.; Wang, J.; Wu, Z.; Lu, Y.; Org. Lett. 2022, 24, 3712.
(b) Li, Y.; Hu, X.; Li, B.; Zhang, S.; Yao, H.; Xiao, X.; Huang, N.; Wang, N.; Org. Lett. 2024, 26, 10651.
(c) Chen, Z.; Xiong, D.; Wang, N.; Zhang, Y.; Yao, H.; Zhang, J.; Huang, N.; Zou, K.; Org. Chem. Front. 2024, 11, 2762.
(d) Zhang, Y.; Chen, J.; Yao, H.; Wang, Y.; Liu, H.; Wang, L. Huang, N.; Wang, N.; Chin. J. Chem. 2025, 43, 995.
(e) Zheng, Y.; Zhao, Y.; Xin, Y.; Qu, X.; Chen, Y.; Xiao, X.; Huang, N. Wang, N. Org. Lett. 2026, 28, 1661.
(f) Chen D.; Wang L.; Yao H.; Gao H.; Hu C.; Wu M.; Lee C.-L. K.; Liu Z.; Huang N.; Wang N. Org. Lett.2026, 28, 7698.
(g) Hu X.; Qu X.; Li Z.; Wang L.; Yao H.; Li L.; Cao Z.-Y.; Huang N.; Wang N. Chem. Commun.2026, 62, 8013-8017.
[6] (a) Cao G.-M.; Yan S.-S.; Song L.; Jiang Y.-X.; Gao T.-Y.; Chen Z.; Zhang W.; Ye J.-H.; Yu, D.-G. Chem. Soc. Rev.2025, 54, 6726.
(b) Wang Y.; Bao Z.-P.; Mao X.-D.; Hou M.; Wu, X.-F. Chem. Soc. Rev.2025, 54, 9530.
(c) Liu Y.; Xu D.; Ping Y.; Wang N.; Kong, W. Chin. Chem. Lett.2026, 37, 111893.
(d) Deng Z.-X.; Liu Z.-G.; Han J.-Y.; Zhou T.-Y.; Cheng D.; Xiao X.; Chen F.-E. Green Chem.2026, 28, 5447
(e) Wang, J.-T.; Li, Y.-H.; Cao, H.-F.; Xu, Y.-Q.; Cao, Z.-Y.; Zhang, P.-F.; Jin, S.Org. Lett. 2026, 28, 2000.
(f) Hu, Z.; Wu, J.; Zhou, L.; Wang, T.Synlett 2026, DOI: 10.1055/a-2851-6160.
(g) Li Y.; You M.; Wu J.-H.; Hu Z.; Lei F.; Mao H.; Wang T.; Zhou, L. J. Org. Chem.2026, 91, 7568.
(h) Wan Q.; Tang M.; Han X.; Lang Y.; Cheng Z.; Wang Y.; Yuan Z. Org. Lett.2026, 28, 5165.
[7] (a) Li S.; Li X.; Yao H.; Tan M.; Xu D.; Huang N.; Wang, N. Org. Chem. Front.2024, 11, 236.
(b) Liu R.; Liu J.; Cao J.; Li R.; Zhou R.; Qian Y.; Gao W.-C. Org. Lett.2020, 22, 6922.
(c) Hu, Y.; Cai, Y.; Liu, Y.; Xiong, D.; Yao, H.; Li, L.; Cao, Z.-Y.; Huang, N.; Wang, N.Chin. J. Chem. 2025, 43, 2181.
(d) Chen G.; Nie G.; Li L.; Fu J.; Yao H.; Huang N.; Wang, N. Org. Chem. Front.2025, 12, 2212.
(e) Liu Y.; Chen Y.; Deng. C.; Yao H.; Li L.; Wang L.; Huang N.; Wang N. Org. Lett.2025, 27, 11503.
[8] Zhou L.; Yuan C.; Zeng Y.; Liu H.; Wang C.; Gao X.; Wang Q.; Zhang C.; Guo H. Chem. Sci.2018, 9, 1831.
[9] Liu M.; Zhou L.; Shi W.; Hu W.; Liao J.; Duan, .Z; Wang W.; Wu Y.; Zheng B.; Guo H. Org. Lett.2021, 23, 7703.
[10] (a) Shi W.; Zhou L.; Mao B.; Wang Q.; Wang C.; Zhang C.; Li X.; Xiao Y.; Guo, H. J. Org. Chem.2019, 84, 679.
(b) Gao Z.; Xie L.; Ji L.; Ma X.; Li X.; Liu H.; Guo H. RSC Adv.2021, 11, 40136.
(c) Maddiggan-Wyatt J. T.; Gao J.; Ametovski J.; Hooper J. F.; Lupton, D. W. Org. Lett.2022, 24, 2847.
[11] (a) Maddigan-Wyatt J. T.; Blith M. T.; Amettovski J.; Coote M. L.; Hooper J. F.; Lupton, D. W. Chem. Eur. J.2021, 27, 16232.
(b) Zhou L.; Zhang X.; Wang Q.; Liu M.; Wang W.; Wu Y.; Chen L.; Guo H. Org. Lett.2021, 23, 9173.
[12] Chen, G.; Chen, D.; Nie, G.; Li, L.; Yao, H.; Wang, N.; Huang, N.Chin. J. Org. Chem. 2025, 45, 2139. (in Chinese)
(陈刚, 陈东, 聂广杰, 李林轩, 姚辉, 王能中, 黄年玉, 有机化学, 2025,45, 2139.)
[13] (a) Pan M.-X.; Chen P.; Jiang, Y.-J. Adv. Synth. Catal.2025, 367, e9605.
(b) Liu Z.; Khan J.; Akram M.; Mumtaz, Y. Chin. J. Org. Chem.2025, 45, 2350. (in Chinese)
(刘尊棋; Khan, J.; Akram M.; Mumtaz, Y. 有机化学,2025, 45, 2350.)
(c) Wang R.; Xu Q.; Hoye, T. R. Org. Lett.2024, 26, 7805.
(d) Lv Y.; Ding H.; You J.; Wei W.; Yi, D. Chin. Chem. Lett.2024, 35, 109107.
[14] (a) An F.; Jangra H.; Wei Y.; Shi M.; Zipse H.; Ofial, A. R. Chem. Commun.2022, 58, 3358.
(b) An F.; Brossette J.; Jangra H.; Wei Y.; Shi M.; Zipse H.; Ofial, A. R. Chem. Sci.2024, 15, 18111.
[15] Meyers A. I.; Schmidt W.; Mchennon M. J. Synthesis1993, 2, 250.
[16] (a) Zhou L.; Zhang X.; Wang Q.; Liu M.; Wang W.; Wu Y.; Chen L.; Guo H. Org. Lett.2021, 23, 9173.
(b) Chen G.; Nie G.; Li L.; Fu J.; Yao H.; Huang N.; Wang, N. Org. Chem. Front.2025, 12, 2212.
(c) Jia, P.; Zhang, Q.; Zhuge, Y.; Liwei, X.; Huang, Y. Adv. Synth. Catal. 2018, 360, 438.
(d) Guard L.; Rizzo, J. Org. Process Res. Dev.2024, 28, 2827.
(e) Fukata, Y.; Asano, K.; Matsubara, S. J. Am. Chem. Soc. 2013, 135, 12160.
(f) Nakagawa Y.; Chanthamath S.; Shibatomi K.; Iwasa S. Org. Lett.2015, 17, 2792.
(g) Zhao, L.; Lin, Y.; Yan, H.; Du, D. Org. Biomol. Chem., 2015, 13, 11351.
(h) Long T.; Gao T.; Chen G.; Kong H.-H.; Yang Q.-Q.; Xu W.; Xiao S.; Ye L.; Wang, L. Chin. J. Chem.2026, 44, 959.
Options
Outlines

/

〈 〉