可见光介导铜催化1,3-烯炔的双官能团化反应进展

doi:10.6023/cjoc202604003

摘要/Abstract

可见光介导铜催化1,3-烯炔的双官能团化反应是构建多取代联烯以及炔丙基化合物的高效策略. 系统综述了近年来可见光介导铜催化1,3-烯炔双官能团化的研究进展, 围绕不同的自由基前体类型, 分类阐述其在1,3-烯炔双官能团化中的应用, 并探讨了反应机理, 选择性调控机制及影响因素以及不对称催化反应进展. 最后, 针对该领域面临的挑战以及未来发展方向进行了总结和展望.

关键词: 光氧化还原催化, 铜催化, 1,3-烯炔, 联烯, 双官能团化

Visible-light-mediated copper-catalyzed 1,3-enyne difunctionalization represents an efficient strategy for the cons- truction of polysubstituted allenes and propargylic compounds. Systematic advances in visible-light-mediated copper-catalyzed difunctionalization of 1,3-enynes in recent years are reviewed. Their applications in the difunctionalization of 1,3-enynes are elaborated by category according to different types of radical precursors. Reaction mechanisms, selectivity regulation mechanisms, influencing factors as well as advances in asymmetric catalytic reactions are discussed. Finally, the existing challenges in this field are outlined, and prospects for future research are proposed.

Key words: photoredox catalysis, copper catalysis, 1,3-enyne, allene, difunctionalization

引用此文

刘佩雯, 叶富, 袁伟明. 可见光介导铜催化1,3-烯炔的双官能团化反应进展[J]. 有机化学, 2026, 46(7): 2563-2580.

Peiwen Liu, Fu Ye, Weiming Yuan. Recent Advances in Visible-Light-Mediated Copper-Catalyzed Difunctionalization of 1,3-Enynes[J]. Chinese Journal of Organic Chemistry, 2026, 46(7): 2563-2580.

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图/表 18

图式1. 可见光介导铜催化1,3-烯炔的双官能团化反应

Scheme 1. Visible-light-mediated copper-catalyzed difunctionalization of 1,3-enynes

图式2. 光/铜协同催化1,3-烯炔的脱羧1,4-碳氰基化反应

Scheme 2. Decarboxylative 1,4-carbocyanation of 1,3-enynes via photoredox/copper dual catalysis

图式3. 光/铜协同催化1,3-烯炔的脱羧不对称1,4-碳氰基化反应

Scheme 3. Enantioselective decarboxylative 1,4-carbocyanation of 1,3-enynes via photoredox/copper dual catalysis

图式4. 光/铜协同催化1,3-烯炔的不对称1,2-碳氰基化反应

Scheme 4. Enantioselective 1,2-carbocyanation of 1,3-enynes via photoredox/copper dual catalysis

图式5. 光/铜协同催化1,3-烯炔的1,4-烷基氰基化反应

Scheme 5. 1,4-Alkylcyanation of 1,3-enynes enabled by photoredox/copper dual catalysis

图式6. 光/铜协同催化1,3-烯炔的1,5-氢原子转移官能团化反应

Scheme 6. Difunctionalization of 1,3-enynes via 1,5-HAT by photoredox/copper dual catalysis

图式7. 光激发铜催化1,3-烯炔、环丁酮肟酯与芳基硼酸的三组分自由基环化反应

Scheme 7. Three-component radical annulation of 1,3-enynes, cyclobutanone oxime esters and arylboronic acids enabled by photoinduced copper catalysis

图式8. 光/铜协同催化1,3-烯炔的三组分1,4-氰烷基芳基化反应

Scheme 8. 1,4-Cyanoalkylarylation of 1,3-enynes enabled by photoredox/copper dual catalysis

图式9. 光诱导铜催化1,3-烯炔不对称脱羧1,2-氰烷基酯化反应

Scheme 9. Enantioselective decarboxylative 1,2-cyanoalkyl esterification of 1,3-enynes enabled by photoinduced copper catalysis

图式10. 光诱导铜催化1,3-烯炔的不对称1,2-氰烷基酯化反应

Scheme 10. Enantioselective 1,2-cyanoalkyl esterification of 1,3-enynes enabled by photoinduced copper catalysis

图式11. 光/铜协同催化1,3-烯炔的酰基/三氟甲硫基化反应

Scheme 11. Acyl-trifluoromethylthiolation of 1,3-enynes enabled by photoredox/copper dual catalysis

图式12. 光/铜协同催化亚砜叶立德介导的1,3-烯炔的烷基氰基化反应

Scheme 12. Photoredox/copper-catalyzed alkylcyanation of 1,3-enynes using sulfoxonium ylides as carbon radical precursors

图式13. 光/铜协同催化噻蒽鎓盐介导的1,3-烯炔1,4-芳基氰基化反应

Scheme 13. Photoredox/copper-catalyzed 1,4-arylcyanation of 1,3-enynes using thianthrenium salts as aryl radical precursors

图式14. 光/铜协同催化1,3-烯炔的1,4-芳基氰基化反应

Scheme 14. 1,4-Arylcyanation of 1,3-enynes enabled by photoredox/copper dual catalysis

图式15. 光/铜协同催化1,3-烯炔的1,4-三氟甲胺基氰基化反应

Scheme 15. 1,4-Trifluoromethylaminocyanation of 1,3-enynes enabled by photoredox/copper dual catalysis

图式16. 光/铜协同催化1,3-烯炔的1,4-酰胺基氰基化反应

Scheme 16. 1,4-Amidocyanation of 1,3-enynes enabled by photoredox/copper dual catalysis

图式17. 光/铜协同催化1,3-烯炔的1,4-全氟烷基氰基化反应

Scheme 17. 1,4-Perfluoroalkylcyanation of 1,3-enynes enabled by photoredox/copper dual catalysis

图式18. 光/铜协同催化1,3-烯炔的1,4-二氟烷基氰基化反应

Scheme 18. 1,4-Difluoroalkylcyanation of 1,3-enynes enabled by photoredox/copper dual catalysis

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