Progress in Copper-Catalyzed Asymmetric Propargylic Substitution/Cyclization Cascades

doi:10.6023/cjoc202605003

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (9): 3506-3522.DOI: 10.6023/cjoc202605003 Previous Articles Next Articles

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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 发布日期:2026-06-03
通讯作者: 丁奎岭, 王晓明
基金资助:
国家重点研发计划(2022YFA1503200); 及中国科学院战略性先导科技专项(XDB1180000)

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 Published:2026-06-03
Contact: Kuiling Ding, Xiaoming Wang
About author:
Dedicated to the 100th anniversary of the birth of Professor Xikui Jiang.
Supported by:
National Key R&D Program of China(2022YFA1503200); Strategic Priority Research Program of the Chinese Academy of Sciences(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. The research progress of copper-catalyzed asymmetric propargylic substitution/cyclization cascade reactions in recent years is systematically summarized.

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

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Xiaolong Chen, Lin Gao, Kuiling Ding, Xiaoming Wang. Progress in Copper-Catalyzed Asymmetric Propargylic Substitution/Cyclization Cascades[J]. Chinese Journal of Organic Chemistry, 2026, 46(9): 3506-3522.

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Fig. & Tab. 26

Scheme 1. Development of copper-catalyzed asymmetric propargylic substitution/annulation cascade reactions

Scheme 2. Copper-catalyzed intermolecular and intramolecular asymmetric propargylic substitution/cyclization cascade reactions

Scheme 3. Copper-catalyzed asymmetric cycloaddition reaction of propargylic esters with cyclic enamines

Scheme 4. A series of copper-catalyzed asymmetric propargylic substitution/cyclization cascade reactions reported by Hu’s group

Scheme 5. Copper-catalyzed asymmetric propargylic substitution/cyclization cascade reaction of trimethylsilyl propargyl acetates

Scheme 6. Copper-catalyzed asymmetric [4＋1] cycloaddition of sulfur ylides with ethynyl benzoxazinones

Scheme 7. Copper/amine cooperative catalyzed asymmetric cyclization of ethynyl benzoxazinones

Scheme 8. Copper-catalyzed asymmetric [4＋2] cycloaddition reactions of ethynyl benzoxazinones

Scheme 9. Copper-catalyzed asymmetric [3＋3] and [4＋3] cycloaddition reactions of ethynyl benzoxazinones

Scheme 10. Copper-catalyzed remote enantioselective propargylic substitution/cycloaddition cascade

Scheme 11. Copper-catalyzed asymmetric [3＋2] cycloaddition of propargylic esters

Scheme 12. Copper-catalyzed asymmetric propargylic amination-carboxylation cyclization cascade reaction

Scheme 13. Copper-catalyzed intermolecular asymmetric propargylic dearomatization

Scheme 14. Asymmetric [3＋2] cycloaddition catalyzed by copper/amine cooperative catalysis

Scheme 15. Strategy reported by Hu’s group for constructing chiral cyclic compounds with quaternary carbon stereocenters

Scheme 16. N-Heterocyclic carbene and copper cooperative catalyzed asymmetric [3＋3] and [3＋4] cyclizations

Scheme 17. Copper-catalyzed asymmetric [3＋2] annulation of ethynylindole oxazolidinones with azlactones

Scheme 18. Copper-catalyzed asymmetric propargylic substitution/cycloaddition cascade reaction of ethynyl vinyl carbonates

Scheme 19. Copper-catalyzed asymmetric propargylic substitution/[3＋2] cycloaddition cascade reaction of ethynyl carbamates

Scheme 20. Copper-catalyzed asymmetric propargylic amination cascade cyclization strategy for the construction of quaternary stereocenters

Scheme 21. Copper-catalyzed asymmetric [3＋3] cycloaddition reaction of ethynylethylene carbonates

Scheme 22. Copper-catalyzed remote enantioselective propargylic substitution for the construction of chiral cyclic compounds bearing quaternary carbon stereocenters

Scheme 23. Chiral dinuclear copper-catalyzed asymmetric propargylation/[3＋2] cycloaddition cascade reaction

Scheme 24. Copper-catalyzed asymmetric [3＋2] cycloaddition reaction of trifluoromethyl-substituted propargyl esters

Scheme 25. Copper-catalyzed asymmetric [4＋3] cycloaddition reaction of ethynylmethylene cyclic carbamates with dienol silyl ethers

Scheme 26. Copper-catalyzed intramolecular propargylic substitution/rearrangement or ring-opening/cyclization reactions

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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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