Recent Progress in Copper-Catalyzed Remote Yne-Allylic Substitution Reaction

doi:10.6023/cjoc202507019

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (2): 356-378.DOI: 10.6023/cjoc202507019 Previous Articles Next Articles

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铜催化远程炔-烯丙基取代反应研究进展

李梦蝶^a^,^†, 王紫涵^a^,^†, 林桃燕^a^,^b^,^*()

^a 淮北师范大学化学与化工学院安徽淮北 235000
^b 贵州大学绿色农药全国重点实验室贵阳 550025

收稿日期:2025-07-15 修回日期:2025-09-25 发布日期:2025-11-15
通讯作者: 林桃燕
作者简介:
^† 共同第一作者
基金资助:
国家自然科学基金(22301095); 及绿色农药全国重点实验室2025年度联合开放课题基金(GPLKF202509)

Recent Progress in Copper-Catalyzed Remote Yne-Allylic Substitution Reaction

Mengdie Li^a, Zihan Wang^a, Taoyan Lin^a^,^b^,^*()

^a School of Chemistry and Chemical Engineering, Huaibei Normal University, Huaibei, Anhui 235000
^b State Key Laboratory of Green Pesticide, Guizhou University, Guiyang 550025

Received:2025-07-15 Revised:2025-09-25 Published:2025-11-15
Contact: Taoyan Lin
About author:
^† These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22301095); Opening Funding of Project of National Key Laboratory of Green Pesticide in 2025(GPLKF202509)

Copper-catalyzed remote yne-allylic substitution system is an efficient approach for constructing functional molecules containing unsaturated bonds, and a variety of new catalytic systems and reaction modes have been successfully developed. Yne-allylic ester substrates with remote leaving groups are converted into copper vinyl-allenylidene intermediates under the cooperative catalysis of copper/ligands. The nucleophilic addition of nucleophiles to the γ-position or ε-position of the intermediates can efficiently construct important skeletons such as structurally diverse 1,3-enynes, 1,4-enynes, allenes, spirocyclic compounds, and C—C/C—N/N—N axially chiral compounds. From the perspective of classification by nucleophile types, the latest research progress of copper-catalyzed remote yne-allylic substitution reactions involving various nucleophiles such as carbon, nitrogen, and sulfur is systematically summarized. It focuses on the discussion of reaction mechanisms and prospects for the future development direction of this field.

Key words: copper-catalysis, yne-allylic substitution, remote, copper vinyl-allenylidene intermediate

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Mengdie Li, Zihan Wang, Taoyan Lin. Recent Progress in Copper-Catalyzed Remote Yne-Allylic Substitution Reaction[J]. Chinese Journal of Organic Chemistry, 2026, 46(2): 356-378.

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Fig. & Tab. 31

Scheme 1. Mechanism of copper-catalyzed yne-allylic substitution reaction

Scheme 2. Copper-catalyzed propargylic substitution of soft nucleophiles

Scheme 3. Asymmetric [4＋1] annulation of 1,3-dicarbonyl compounds

Scheme 4. Remote asymmetric dearomatization and rearomatization via alkynyl copper driven

Scheme 5. Enantioselective [4＋1] and [3＋3] cycloaddition of ethynylethylene carbonates

Scheme 6. Asymmetric yne-allylic substitution of electron-rich arenes

Scheme 7. Remote enantioselective substitution of yne-thiophene carbonates

Scheme 8. Asymmetric alkynylallylic monofluoroalkylations of fluorinated malonates

Scheme 9. Enantioselective [4＋1] spiroannulation of nonfunctionalized 1‑naphthols

Scheme 10. Dearomative spiroannulation of β‑naphthols or indoles

Scheme 11. Asymmetric yne-allylic substitution of anthrones

Scheme 12. Dual remote asymmetric yne-allylic substitution of coumarins

Scheme 13. Asymmetric yne-allylic substitution of 4-methylcoumarin

Scheme 14. Asymmetric yne-allylic substitution of thiazolone derivatives

Scheme 15. Asymmetric yne-allylic substitution of pyrazolones

Scheme 16. Copper catalyzed asymmetric yne-allylic amination

Scheme 17. Asymmetric yne-allylic dimethylamination

Scheme 18. Asymmetric yne-allylic substitution via carbon dioxide shuttling and fixation

Scheme 19. Asymmetric annulation of amines to access axially chiral arylpyrroles

Scheme 20. Catalytic synthesis of pyrroles from vinyl ethynylethylene carbonates

Scheme 21. Copper-catalyzed [4＋1] and [4＋2] reactions involving amines or hydrazines

Scheme 22. Larock-type cyclization/debenzylation of aliphatic amines

Scheme 23. Asymmetric annulation catalyzed via cooperative copper-squaramide catalysis

Scheme 24. Atroposelective synthesis of N—N axially chiral compounds bearing minimally different alkyl groups

Scheme 25. Remote enantioselective sulfonylation of sodium sulfonates

Scheme 26. Ligand-controlled copper-catalyzed regiodivergent sulfonylation

Scheme 27. Enantioselective functionalization of unactivated C(sp3)—H bonds through copper-catalyzed diyne cyclization via kinetic resolution

Scheme 28. Copper-catalyzed intramolecular formal one-carbon insertion reaction

Scheme 29. Copper-catalyzed diyne cyclization for asymmetric one-carbon ring expansion of diverse N-heterocycles

Scheme 30. Copper-catalyzed ligand-controlled divergent asymmetric insertion reaction via vinyl cations

Scheme 31. Copper-catalyzed enantioselective C(sp²)—H functionalization of (hetero)arenes with vinyl cations

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铜催化远程炔-烯丙基取代反应研究进展

Recent Progress in Copper-Catalyzed Remote Yne-Allylic Substitution Reaction

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