一价铜催化的酮或酮亚胺的不对称烯丙基化反应研究进展

doi:10.6023/A24100300

摘要/Abstract

手性高烯丙基叔醇和相应的高烯丙基胺结构单元广泛存在于天然产物和药物分子中. 因此, 其不对称合成受到合成化学家们的重视. 过渡金属催化的酮或酮亚胺的不对称烯丙基化反应具有优秀的原子经济性和步骤经济性, 是合成手性高烯丙基叔醇和相应的高烯丙基胺最直接有效的方法之一. 此综述着重介绍了一价铜催化的酮或酮亚胺不对称烯丙基化反应的研究进展. 根据生成烯丙基一价铜物种的不同方式, 将反应分为转金属化反应、三组分偶联反应和质子转移反应. 另外, 对一些具有代表性的反应机理和产物的合成应用做了简要介绍, 并对该领域的发展进行了展望.

关键词: 一价铜催化, 酮, 酮亚胺, 不对称烯丙基化反应, 转金属化反应, 三组分偶联反应, 质子转移反应

Chiral tertiary homoallylic alcohol and chiral α,α-disubstituted homoallylic amine scaffolds are ubiquitous in numerous bioactive natural products and pharmaceutically relevant molecules. Thus, asymmetric synthesis of these compounds has attracted an increasing attention from synthetic chemists. Compared to traditional methods, transition-metal-catalyzed asymmetric allylation of ketones or ketimines serves as a powerful methodology for constructing these compounds due to its excellent atom- and step-economy. Recent progress on copper(I)-catalyzed asymmetric allylation of ketones or ketimines is summarized. Based on the strategies for the generation of allyl-copper(I) species in situ, this review is divided into three sections: reactions through transmetalation, three-component coupling reactions, and proton-transfer reactions. The mechanisms and potential applications of some representative strategies are also included. Finally, the future developments in this field are outlooked.

Key words: copper(I) catalysis, ketones, ketimines, asymmetric allylation, transmetalation, three-component coupling, proton-transfer reaction

引用此文

李晖, 殷亮. 一价铜催化的酮或酮亚胺的不对称烯丙基化反应研究进展[J]. 化学学报, 2024, 82(12): 1274-1288.

Hui Li, Liang Yin. Research Progress on Copper(I)-Catalyzed Asymmetric Allylation of Ketones or Ketimines[J]. Acta Chimica Sinica, 2024, 82(12): 1274-1288.

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图/表 24

图式1. 一价铜催化的酮或酮亚胺不对称烯丙基化反应策略

Scheme 1. Strategies in copper(I)-catalyzed asymmetric allylation of ketones or ketimines

图式2. 一价铜催化的烯丙基硅烷或烯丙基硼酸酯与酮的不对称加成反应

Scheme 2. Copper(I)-catalyzed asymmetric addition of allylsilanes or allylboronates to ketones

图式3. 一价铜催化的3,3-二取代烯丙基二硼化合物与酮的不对称加成反应

Scheme 3. Copper(I)-catalyzed asymmetric addition of 3,3-disubstituted allyldiboronates to ketones

图式4. 一价铜催化的烯丙基硼酸酯与酮的动态动力学不对称烯丙基化反应

Scheme 4. Copper(I)-catalyzed dynamic kinetic asymmetric allylation of ketones with allylboronates

图式5. 一价铜催化的烯丙基硼酸酯与酮亚胺的不对称加成反应

Scheme 5. Copper(I)-catalyzed asymmetric addition of allylboronate to ketimines

图式6. 一价铜催化的酮、联烯与含氢硅烷的不对称三组分偶联反应

Scheme 6. Copper(I)-catalyzed asymmetric three-component coupling reaction of ketones, allenes, and hydrosilanes

图式7. 一价铜催化的酮与联烯基硅烷的不对称还原偶联反应

Scheme 7. Copper(I)-catalyzed asymmetric reductive coupling reaction of ketones and allenylsilanes

图式8. 一价铜催化的酮与环状联烯酰胺的不对称还原偶联反应

Scheme 8. Copper(I)-catalyzed asymmetric reductive coupling reaction of ketones and a cyclic allenamide

图式9. 一价铜催化的酮与非环状联烯酰胺的不对称还原偶联反应

Scheme 9. Copper(I)-catalyzed asymmetric reductive coupling reaction of ketones and an acyclic allenamide

图式10. 一价铜催化的酮与硅氧基丙二烯的不对称还原偶联反应

Scheme 10. Copper(I)-catalyzed asymmetric reductive coupling reaction of ketones and siloxypropadienes

图式11. 一价铜催化的酮与共轭二烯的不对称还原偶联反应

Scheme 11. Copper(I)-catalyzed asymmetric reductive coupling reaction of ketones with conjugated dienes

图式12. 一价铜催化的含有共轭二烯基团酮的分子内不对称还原偶联反应

Scheme 12. Copper(I)-catalyzed asymmetric intramolecular reductive coupling reaction of conjugated diene-tethered ketones

图式13. 一价铜催化的酮与氮杂三烯的不对称还原偶联反应

Scheme 13. Copper(I)-catalyzed asymmetric reductive coupling reaction of ketones and azatrienes

图式14. 一价铜催化的连有共轭二烯基团酮亚胺的分子内不对称还原偶联反应

Scheme 14. Copper(I)-catalyzed asymmetric intramolecular reductive coupling reaction of conjugated diene-tethered ketimines

图式15. 铜氢物种催化的共轭二烯与酮亚胺的不对称还原偶联反应

Scheme 15. CuH-catalyzed asymmetric reductive coupling reaction of ketimines with conjugated dienes

图式16. 一价铜催化的酮、联烯和联硼酸酯的不对称偶联反应

Scheme 16. Copper(I)-catalyzed asymmetric coupling reaction of ketones, allenes, and B2(pin)2

图式17. 一价铜催化的联烯基环己二酮的不对称硼化环化反应

Scheme 17. Copper(I)-catalyzed asymmetric borylative cyclization of allene cyclohexanediones

图式18. 一价铜催化的联烯与酮亚胺、联硼酸频哪醇酯的不对称碳硼化反应

Scheme 18. Copper(I)-catalyzed asymmetric carboboronation of allenes with ketimines and B2(pin)2

图式19. 一价铜催化的联烯与酮亚胺酯、联硼酸频哪醇酯的不对称碳硼化反应

Scheme 19. Copper(I)-catalyzed asymmetric carboboronation of allenes with ketiminoesters and B2(pin)2

图式20. 一价铜催化的1,3-二烯与酮的不对称硼化偶联反应

Scheme 20. Copper(I)-catalyzed asymmetric borylative coupling reaction of 1,3-dienes with ketones

图式21. 一价铜催化的含有共轭二烯基团酮的不对称硼化环化反应

Scheme 21. Copper(I)-catalyzed asymmetric borylative cyclization of conjugated dienes-tethered ketones

图式22. 一价铜催化的酮与1,4-烯炔的不对称烯丙基化反应

Scheme 22. Copper(I)-catalyzed asymmetric allylation reaction of ketones with 1,4-enynes

图式23. 一价铜催化的酮与1,4-二烯的立体选择性烯丙基化反应

Scheme 23. Copper(I)-catalyzed stereoselective allylation reaction of ketones with 1,4-dienes

图式24. 一价铜催化的酮与2-氮杂-1,4-二烯的不对称烯丙基化反应

Scheme 24. Copper(I)-catalyzed asymmetric allylation reaction of ketones with 2-aza-1,4-dienes

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