1,3-烯炔双官能团化反应研究进展

doi:10.6023/cjoc202502004

摘要/Abstract

1,3-烯炔是一类同时具有烯基和炔基的有机分子, 由于其独特的结构特性, 已被用作多种反应的基本单元, 以获得各种特殊的分子结构. 1,3-烯炔的选择性双官能团化反应是构建1,3-二烯型化合物、炔基化合物、噻吩和吡咯等芳香杂环以及多取代丙二烯衍生物的一种极具吸引力的策略. 近年来, 1,3-烯炔的双官能团化策略已被广泛报道, 然而控制其化学和区域选择性双官能团化的挑战一直存在. 综述了近几年1,3-烯炔的1,2-、3,4-和1,4-双官能化反应, 并对该领域的发展方向进行了展望.

关键词: 1,3-烯炔, 双官能团化, 炔基化合物, 丙二烯衍生物, 1,3-二烯

1,3-Enynes are a class of organic molecules with both alkyl and alkenyl groups, which have unique structural properties and have been used as the basic units in a variety of reactions to obtain a variety of specialized molecular structures. Selective difunctionalization of 1,3-enynes is an attractive strategy for the construction of 1,3-diene-type compounds, alkyne-based compounds, aromatic heterocycles such as thiophenes and pyrroles, as well as multisubstituted allene derivatives. In recent years, various catalytic strategies for the difunctionalization of 1,3-enynes have been widely reported, however, challenges in controlling the chemo- and regioselective difunctionalization of 1,3-enynes persist. The 1,2-, 3,4-, and 1,4-difunctionalization reactions of 1,3-enynes in the last few years are summarized, and the directions of development in this field are prospected.

Key words: 1,3-enyne, difunctionalization, alkynyl compound, allene derivative, 1,3-diene

引用此文

孙良龙, 孙凯. 1,3-烯炔双官能团化反应研究进展[J]. 有机化学, 2025, 45(10): 3655-3671.

Lianglong Sun, Kai Sun. Recent Progress on the Difunctionalization Reaction of 1,3-Enynes[J]. Chinese Journal of Organic Chemistry, 2025, 45(10): 3655-3671.

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图/表 32

图式1. 1,3-烯炔双官能化反应的主要类型

Scheme 1. Main types of difunctionalization of 1,3-enynes

图式2. 铜/二叔丁基过氧化物催化的1,3-烯炔的1,2-羟基化磷酸化反应

Scheme 2. Copper/Di-tert-butyl peroxide-catalyzed 1,2-hydroxy and phosphorylation of 1,3-enynes

图式3. 铜(I)催化的1,3-烯炔的不对称1,3-偶极环加成反应

Scheme 3. Copper(I)-catalyzed asymmetric 1,3-dipole cycloadditions of 1,3-enynes

图式4. 光、铜催化1,3-烯炔的三组分自由基交叉偶联反应

Scheme 4. Photo-, copper-catalyzed three-component radical cross-coupling reactions of 1,3-enynes

图式5. 光诱导铬催化的1,3-烯炔的非对映选择性1,2-双烷基化反应

Scheme 5. Photoinduced chromium-catalyzed diastereoselective 1,2-dialkylation of 1,3-enynes

图式6. 铜催化氮宾插入的1,3-烯炔1,2-双官能化反应

Scheme 6. Copper-catalyzed 1,2-difunctionalization of 1,3-enynes via nitroxide insertions

图式7. 三硫自由基阴离子($\text{SO}{{_{3}^{}}^{-\ \bullet }}$)参与的1,3-烯炔的硫插入反应

Scheme 7. Sulfur insertion reaction of 1,3-enynes involving trisulfur radical anion ($\text{SO}{{_{3}^{}}^{-\ \bullet }}$)

图式8. 1,3-烯炔的选择性二氟甲基硫/硒代化反应

Scheme 8. Selective difluoromethyl sulfur/selenocyclization of 1,3-enynes

图式9. 钯催化1,3-烯炔的3,4-反式选择性硼氰化反应

Scheme 9. Palladium-catalyzed 3,4-trans-selective boron cyanidation of 1,3-enynes

图式10. 钯催化1,3-烯炔的3,4-顺式碳硼化反应

Scheme 10. Palladium-catalyzed 3,4-cis-carboboration of 1,3-enynes

图式11. 钯催化下1,3-烯炔的3,4-顺式双官能化反应

Scheme 11. Palladium-catalyzed 3,4-cis-difunctionalization of 1,3-enynes

图式12. 钯催化1,3-烯炔与亚胺和邻位乙烯基的3,4-双官能化反应

Scheme 12. Palladium-catalyzed 3,4-difunctionalization of 1,3-enynes with imines and adjacent vinyl groups

图式13. 光/镍催化1,3-烯炔的3,4-/1,4-芳基化磺酰化反应

Scheme 13. Photo-/nickel-catalyzed 3,4-/1,4-arylation and sulfonylation of 1,3-enynes

图式14. 铜催化1,3-烯炔的1,4-烷基化芳基化反应

Scheme 14. Copper-catalyzed 1,4-alkylarylation of 1,3-enynes

图式15. 铜/钯催化1,3-烯炔的1,4-芳基硼化反应

Scheme 15. Copper-/palladium-catalyzed 1,4-arylboration of 1,3-enynes

图式16. 无金属催化的1,3-烯炔的1,4-氟胺化反应

Scheme 16. Metal-free catalyzed 1,4-fluoroamination of 1,3- enynes

图式17. 铜催化1,3-烯炔的1,4-对映选择性氧氰化反应

Scheme 17. Copper-catalyzed 1,4-enantioselective oxycyana- tion of 1,3-enynes

图式18. 铜催化1,3-烯炔的1,4-双(三氟甲基化)反应

Scheme 18. Copper-catalyzed 1,4-bis(trifluoromethylation) of 1,3-enynes

图式19. N-杂环卡宾催化的1,3-烯炔的1,4-烷基酰化反应

Scheme 19. N-Heterocyclic carbene-catalyzed 1,4-alkylacylation of 1,3-enynes

图式20. 铜催化1,3-烯炔的1,4-卤化三氟甲基化反应

Scheme 20. Copper-catalyzed 1,4-halogenated trifluoromethylation of 1,3-enynes

图式21. 铜催化1,3-烯炔的1,4-硒基磺酰化反应

Scheme 21. Copper-catalyzed 1,4-selenosulfonylation of 1,3-enynes

图式22. 钯催化1,3-烯炔的1,4-羧化芳基化反应

Scheme 22. Palladium-catalyzed 1,4-carboxyaromatization of 1,3-enynes

图式23. 光/铬催化1,3-烯炔的不对称1,4-双官能化反应

Scheme 23. Photo-/chromium-catalyzed asymmetric 1,4-difunctionalization of 1,3-enynes

图式24. 铜催化1,3-烯炔的区域选择性1,4-磺酰氰化反应

Scheme 24. Copper-catalyzed regioselective 1,4-sulfonyl cyanation of 1,3-enynes

图式25. 光/铜催化1,3-烯炔的三氟甲基氨基氰化反应

Scheme 25. Photo-/copper-catalyzed trifluoromethylaminocyanation of 1,3-enynes

图式26. 无金属催化的1,3-烯炔区域选择性1,4-磺酰化碘化反应

Scheme 26. Metal-free catalyzed regioselective 1,4-sulfonyl iodination of 1,3-enynes

图式27. 钴催化1,3-烯炔的1,4-羧化磺酰基化反应

Scheme 27. Cobalt-catalyzed 1,4-carboxy sulfonylation of 1,3- enynes

图式28. 电催化1,3-烯炔的区域选择性芳基烷基化、二烷基化和氢(氘)烷基化反应

Scheme 28. Electrocatalytic regionally selective aryl alkylation, dialkylation and hydrogen (deuterium) alkylation of 1,3-enynes

图式29. 光/镍催化1,3-烯炔的1,4-芳基烷基化反应

Scheme 29. Photo-/nickel-catalyzed 1,4-arylalkylation of 1,3-enynes

图式30. 光/铜催化1,3-烯炔的1,4-双(三氟甲基化)反应

Scheme 30. Photo-/copper-catalyzed 1,4-bis(trifluoromethylation) of 1,3-enynes

图式31. 镍/电催化1,3-烯炔的1,4-双官能团化反应

Scheme 31. Nickel/electrocatalyzed 1,4-difunctionalization of 1,3-enynes

图式32. 钯催化1,3-烯炔的多组分三氟甲基化羰基化反应

Scheme 32. Palladium-catalyzed multicomponent trifluoromethyl carbonylation of 1,3-enynes

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