Progress in Copper-Catalyzed Asymmetric Propargylic Substitution/Cyclization Cascades

doi:10.6023/cjoc202605003

Chinese Journal of Organic Chemistry

ARTICLE

铜催化不对称炔丙基取代/环化串联反应研究进展

陈小龙^a,b, 高琳^b, 丁奎岭^a,b,c,*, 王晓明^b,d,*

^a上海科技大学物质科学与技术学院上海 201210;
^b中国科学院上海有机化学研究所上海 200032;
^c上海交通大学化学化工学院上海 200240;
^d中国科学院大学杭州高等研究院杭州 310024

收稿日期:2026-05-06 修回日期:2026-05-22
基金资助:
国家重点研发计划（2022YFA1503200）、中国科学院战略性先导科技专项（XDB1180000）资助项目

Progress in Copper-Catalyzed Asymmetric Propargylic Substitution/Cyclization Cascades

Xiaolong Chen^a,b, Lin Gao^b, Kuiling Ding^a,b,c,*, Xiaoming Wang^b,d,*

^a School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210;
^b Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032;
^c School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240;
^d Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou 310024

Received:2026-05-06 Revised:2026-05-22
Contact: ^*E-mail: kding@sioc.ac.cn; xiaoming@sioc.ac.cn
Supported by:
National Key R&D Program of China (No. 2022YFA1503200), the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant No. XDB1180000).

Copper-catalyzed asymmetric propargylic substitution/cyclization cascade reactions have become one of the important methods for constructing chiral cyclic compounds due to their advantages such as mild conditions and high enantioselectivity. The key to this reaction lies in the formation of a copper-allenylidene intermediate, which is subsequently captured by a bis-nucleophile, followed by cascade cyclization, enabling the efficient construction of structurally diverse chiral heterocyclic compounds. This review systematically summarizes the research progress of copper-catalyzed asymmetric propargylic substitution/cyclization cascade reactions in recent years.

Key words: copper catalysis, asymmetric propargylic substitution, cyclization reaction, tertiary carbon stereocenter, quaternary carbon stereocenter

Cite this article

Xiaolong Chen, Lin Gao, Kuiling Ding, Xiaoming Wang. Progress in Copper-Catalyzed Asymmetric Propargylic Substitution/Cyclization Cascades[J]. Chinese Journal of Organic Chemistry, doi: 10.6023/cjoc202605003.

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[1] (a) Ljungdahl, N.; Kann, N.Angew. Chem., Int. Ed. 2009, 48, 642.(b) Miyake, Y.; Uemura, S.; Nishibayashi, Y. ChemCatChem 2009, 1, 342. 2009, 6263.(d) Ding C.-H.; Hou X.-L. Chem. Rev.2011, 111, 1914. (e) Sakata, K.; Nishibayashi, Y. Catal. Sci. Technol. 2018, 8, 12., e202300728.
[2] Detz R. J.; Delville M. M.E.; Hiemstra, H.; van Maarseveen, J. H.Angew. Chem., Int. Ed. 2008, 47, 3777.
[3] Hattori G.; Matsuzawa H.; Miyake Y.; Nishibayashi Y.Angew. Chem., Int. Ed. 2008, 47, 3781.
[4] (a) Zhang D.-Y.; Hu X.-P. Tetrahedron Lett.2015, 56, 283.(b) Li, M.-D.; Wang, X.-R.; Lin, T.-Y. Tetrahedron Chem. 2024, 11, 100082.
[5] Hattori G.; Miyake Y.; Nishibayashi Y. ChemCatChem2010, 2, 155.
[6] Shibata M.; Nakajima K.; Nishibayashi Y. Chem. Commun.2014, 50, 7874.
[7] Zhang C.; Hu X.-H.; Wang Y.-H.; Zheng Z.; Xu J.; Hu, X.-P. J. Am. Chem. Soc.2012, 134, 9585.
[8] Zhu F.-L.; Wang Y.-H.; Zhang D.-Y.; Xu J.; Hu X.-P.Angew. Chem., Int. Ed. 2014, 53, 10223.
[9] (a) Zhang D.-Y.; Shao L.; Xu J.; Hu X.-P. ACS Catal.2015, 5, 5026.(b) Chen X.; Hou C.; Li Q.; Liu Y.; Yang R.; Hu, X. Chin. J. Catal.2016, 37, 1389. (c) Liu, Z.-T.; Wang, Y.-H.; Zhu, F.-L.; Hu, X.-P. Org. Lett. 2016, 18, 1190., 5433.
[10] Shao L.; Wang Y.-H.; Zhang D.-Y.; Xu J.; Hu, X.-P. Angew. Chem., Int. Ed.2016, 55, 5014.
[11] Li L.; Liu Z.-T.; Hu X.-P. Chem. Commun.2018, 54, 12033.
[12] Wang Q.; Li T.-R.; Lu L.-Q.; Li M.-M.; Zhang K.; Xiao, W.-J. J. Am. Chem. Soc.2016, 138, 8360.
[13] Song J.; Zhang Z.-J.; Gong, L.-Z. Angew. Chem., Int. Ed.2017, 56, 5212.
[14] Lu X.; Ge L.; Cheng C.; Chen J.; Cao W.; Wu, X. Chem. Eur. J.2017, 23, 7689.
[15] Zhang Y.-C.; Zhang Z.-J.; Fan L.-F.; Song J. Org. Lett.2018, 20, 2792.
[16] Chen H.; Lu X.; Xia X.; Zhu Q.; Song Y.; Chen J.; Cao W.; Wu X. Org. Lett.2018, 20, 1760.
[17] Ji D.; Wang C.; Sun J. Org. Lett.2018, 20, 3710.
[18] (a) Jiang F.; Feng X.; Wang R.; Gao X.; Jia H.; Xiao Y.; Zhang C.; Guo H. Org. Lett.2018, 20, 5278.(b) Wang Y.; Zhu L.; Wang M.; Xiong J.; Chen N.; Feng X.; Xu Z.; Jiang X. Org. Lett.2018, 20, 6506.
[19] Kong H.-H.; Zhu C.; Deng S.; Xu G.; Zhao R.; Yao C.; Xiang H.-M.; Zhao C.; Qi X.; Xu H.J. Am. Chem. Soc. 2022, 144, 21347.
[20] Luo D.; Niu S.; Gong F.; Xu C.; Lan S.; Liu J.; Yang S.; Fang X. ACS Catal.2024, 14, 2746.
[21] Wang Z.-H.; Liu R.-X.; Liu Y.-X.; Liu X.-C.; Cao K.; Lin T.-Y. Org. Lett.2026, 28, 1412.
[22] Dai X.-K.; Xiong J.-X.; Wang Z.-Y.; Qian H.-D.; Zhao J.; Zhou S.; Xu H. Chin. Chem. Lett. 2026, DOI: 10.1016/j.cclet.2026.112870.
[23] Geng Z.-Q.; Zhao C.; Qian H.-D.; Li S.-J.; Peng H.; Xu H. Org. Lett.2023, 25, 4504.
[24] Rohilla S.; Shah S.; Singh, V. K. Org. Lett.2023, 25, 3733.
[25] Li Z.-H.; Ma J.-S.; Lu H.-Y.; Lin G.-Q.; He Z.-T. ACS Catal.2024, 14, 11646.
[26] Lan Y.; Liu P.; Fang Z.; Shao L.; Cai Q.; Wang, X. Org. Chem. Front.2024, 11, 6319.
[27] Shao W.; Li H.; Liu C.; Liu C.-J.; You, S.-L. Angew. Chem., Int. Ed.2015, 54, 7684.
[28] Shao W.; You, S.-L. Chem. Eur. J.2017, 23, 12489.
[29] Zhang Y.-C.; Zhang B.-W.; Geng R.-L.; Song J. Org. Lett.2018, 20, 7907.
[30] Xu Y.-W.; Hu X.-P. Org. Lett.2019, 21, 8091.
[31] Xu Y.-W.; Li L.; Hu X.-P. Org. Lett.2020, 22, 9534.
[32] Zhang Z.-J.; Zhang L.; Geng R.-L.; Song J.; Chen X.-H.; Gong, L.-Z. Angew. Chem., Int. Ed.2019, 58, 12190.
[33] Zhang J.; Ni T.; Yang W.-L.; Deng W.-P. Org. Lett.2020, 22, 4547.
[34] Wang M.; Li B.; Gong B.; Yao H.; Lin A. Chem. Commun.2022, 58, 2850.
[35] Zuo S.; Tao Y.; Liu Z.; Zhang K.; Zhang L.; Ning Y.; Chen F.-E. Org. Lett.2023, 25, 410.
[36] Zhu H.; Xu L.; Zhu B.; Liao M.; Li J.; Han Z.; Sun J.; Huang H. Org. Lett.2023, 25, 9213.
[37] Wang T.; You Y.; Wang Z.-H.; Zhao J.-Q.; Zhang Y.-P.; Yin J.-Q.; Zhou M.-Q.; Cui B.-D.; Yuan W.-C. Org. Lett.2023, 25, 1274.
[38] Battula S.; Kothuri P.; Bhumannagari H.; Nayani, K. Org. Biomol. Chem.2024, 22, 1671.
[39] (a) Zhang Z.; Sun Y.; Gong Y.; Tang D.-L.; Luo H.; Zhao Z.-P.; Zhou F.; Wang X.; Zhou J. Nat. Chem.2024, 16, 521.(b) Zhang, Z.; Zhang, Z. H.; Sun, Y.; Tang, Y. H.; Yang, Y. Z.; Zhou, F.; Zhou, J. Sci. China Chem., 2025, 68, 1402.
[40] Zhang Y.; Shu X.; Guo W. Org. Chem. Front. 2024, 11, 1996.
[41] Chen P.; Zhang M.-M.; Rao L.; Li Y.-H.; Jia Y.; Tan Y.; Xiao W.-J.; Lu L.-Q. Sci. Bull.2024, 69, 3516.
[42] (a) Xu G.; Zhu C.; Li X.; Zhu K.; Xu, H. Chin. Chem. Lett.2025, 36, 110114.(b) Zhao, R.; Deng, S.; Huang, R.; Kong, H.-H.; Lu, Y.; Yin, T.; Wang, J.; Li, Y.; Zhu, C.; Pan, F.; Qi, X.; Xu, H. ACS Catal. 2024, 14, 9254.
[43] Li X.; Guo J.-X.; Zhang J.; Chen Q.-Y.; He Y.-J.; Sha F.; Xiang H.; Yu P.; Liu P.-N. ACS Catal.2024, 14, 9244.
[44] Guo J.; He Y.; Cheng X.; Xiang H.; Li X. Org. Lett.2025, 27, 10700.
[45] (a) Cai Q.; Rao H.; Li S.-J.; Lan Y.; Ding K.; Wang X. Chem2024, 10, 265.(b) Shao, L.; Fang, Z.; Liu, P.; Lan, Y.; Cai, Q.; Wang, X. Nat. Commun. 2025, 16, 7191.
[46] Rohilla S.; Khan Z. A.; Singh, V. K. Org. Biomol. Chem.2025, 23, 2731.
[47] Shen L.; Lin Z.; Guo B.; Zi W. Nat. Synth.2022, 1, 883.
[48] Gong F.; Meng X.; Lan S.; Liu J.; Yang S.; Fang X. ACS Catal.2022, 12, 12036.
[49] Zhao Y.; Yan H.; Jiang Y.; Yang J.; Su X.; Qiao Z.; Zhou W.; He L.; Qiu H.; Zhang M. Chem. Sci.2024, 15, 10963.
[50] (a) Ge Z.; Zhu C.; Xu G.; Guan S.-N.; Xu H. Org. Lett.2025, 27, 5632.(b) Liao M.; Li J.; Zhu H.; Han Z.; Zhang Y.; Sun J.; Huang H. Org. Lett.2025, 27, 4836.

铜催化不对称炔丙基取代/环化串联反应研究进展

Progress in Copper-Catalyzed Asymmetric Propargylic Substitution/Cyclization Cascades

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