自由基形式烯烃双烷基化反应研究进展

doi:10.6023/cjoc202312020

摘要/Abstract

烯烃双官能团化反应是实现烯烃衍生化并构建分子多样的重要方法, 通过双烷基化反应在烯烃两个碳原子上连续构建C(sp³)—C(sp³)键是最有效的功能性烷基化合物的构建方法之一. 由于烷基化试剂活性较高, 烯烃烷基化反应通常伴随着区域选择性差、副反应多等问题. 近十年来, 随着自由基反应研究的深入发展, 自由基形式的烯烃双官能团化反应取得了重要进展, 而实现高选择性双烷基化反应依然存在挑战. 旨在对自由基形式的烯烃双烷基化反应进行一个详尽地总结, 从分子内环化-分子间偶联反应, 烯基硼盐自由基加成、1,2-烷基迁移反应, 差异性烷基化试剂和烯烃三组分烷基化反应这三种不同的反应模式中阐述如何实现高区域选择性烯烃双烷基化过程.

关键词: 烯烃双烷基化, 区域选择性, 烷基自由基, 过渡金属催化, 光催化

Difunctionalization of alkenes constitutes a critical route for alkene derivatization and construction of molecular complexities. Yet dialkylation of alkenes allows the continuous construction of two new C(sp³)—C(sp³) bonds which is one of the most effective ways for functional alkane synthesis. Because of the high reactivity of alkyl reagents, problems such as poor regioselectivity and side reactions always appear in alkene alkylation process. In recent ten years, with the further development in radical mediated reactions, significant progress has been seen in difunctionalization of alkenes through radical path. However, challenges still exist in the implement of high selectively dialkylation of alkenes. This review aims to give a comprehensive overview about the radical involved alkene dialkylated reaction. The regioselectivity control of this reaction is elaborated from three different reaction modes: intramolecular cyclization-intermolecular alkylation, alkyl radical addition-1,2-migrated alkylation of alkenyl boron ate complexes and three-components reaction of alkenes with disparate alkylated reagents.

Key words: alkene diakylation, regioselectivity, alkyl radical, transition-metal catalysis, photocatalysis

引用此文

陆玲依, 邱晓东. 自由基形式烯烃双烷基化反应研究进展[J]. 有机化学, 2024, 44(6): 1701-1718.

Lingyi Lu, Xiaodong Qiu. Recent Progress in Radical Involved Alkene Dialkylation[J]. Chinese Journal of Organic Chemistry, 2024, 44(6): 1701-1718.

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图/表 32

图式1. 烯烃区域选择性双烷基化反应的策略

Scheme 1. General strategies for regioselective dialkylation of alkenes

图式2. 碘代烯烃和烷基溴化锌的分子内环化-烷基化反应

Scheme 2. Intramolecular cyclization-alkylation reaction of alkene containing alkyl iodides and alkyl zinc bromides

图式3. 碘代烯烃和烷基镁试剂的分子内环化-烷基化反应

Scheme 3. Intramolecular cyclization-alkylation reaction of alkene containing alkyl iodides and alkyl magnesium reagents

图式4. 溴代烯烃和烷基溴化物的分子内环化-烷基化反应

Scheme 4. Intramolecular cyclization-alkylation reaction of alkene containing alkyl bromides with alkyl bromides

图式5. 烷基氧化还原活性酯和烷基锌试剂的分子内环化-烷基化反应

Scheme 5. Intramolecular cyclization-alkylation reaction of alkene containing alkyl redox-active esters with alkyl zinc regents

图式6. 分子内烯烃双烷基化环化反应

Scheme 6. Intramolecular dialkylation and cyclization of alkenes

图式7. Et3B引发的烯基硼盐双烷基化反应

Scheme 7. Et3B initiated dialkylation of alkenyl boron ate complexes

图式8. 自由基加成、硼盐1,2-迁移实现烯烃双烷基化反应机理

Scheme 8. Reaction mechanism of alkene dialkylation via continues radical addition and 1,2-migration of boron ates

图式9. Et3B和DTBHN引发的烯基硼盐双烷基化反应

Scheme 9. Et3B and DTBHN initiated dialkylation of alkenyl boron ate complexes

图式10. 光引发的烯基硼盐双烷基化反应

Scheme 10. Photo initiated dialkylation of alkenyl boron ate complexes

图式11. 光引发的烯基硼盐双烷基化反应机理

Scheme 11. Mechanism of photo initiated dialkylation of alke- nyl boron ate complexes

图式12. 光引发烯基硼盐双烷基化反应构建缩环产物

Scheme 12. Photo initiated dialkylation of alkenyl boron ate complexes with the construction of ring-contracted products

图式13. 光催化烯基硼盐双烷基化反应合成邻二硼化物

Scheme 13. Photocatalyzed dialkylation of alkenyl boron ate complexes with the synthesis of ortho-diboron products

图式14. 钴催化1,3-共轭二烯区域选择性双烷基化反应及机理

Scheme 14. Cobalt-catalyzed regioselective dialkylation of 1,3- conjugated dienes and reaction mechanism analysis

图式15. 钛催化苯乙烯衍生物区域选择性双烷基化反应及机理

Scheme 15. Titanium-catalyzed regioselective dialkylation of styrene derivatives and reaction mechanism analysis

图式16. 镍催化已烯基硼酸酯区域选择性双烷基化反应

Scheme 16. Nickel-catalyzed regioselective dialkylation of vinyl boronates

图17. 镍催化乙烯基硼酸酯和溴代烷烃区域选择性双烷基化反应

Scheme 17. Nickel-catalyzed regioselective dialkylation of terminal alkenes with alkyl bromides

图式18. 铜催化末端烯烃区域选择性双烷基化反应

Scheme 18. Copper-catalyzed regioselective dialkylation of terminal alkenes

图式19. 铜催化芳基乙烯区域选择性双烷基化反应

Scheme 19. Copper-catalyzed regioselective dialkylation of arylethylenes

图式20. 镍催化烯丙基酰胺区域选择性双烷基化反应

Scheme 20. Nickel-catalyzed regioselective dialkylation of allyl amides

图式21. 镍催化芳基烯烃区域选择性双烷基化反应

Scheme 21. Nickel-catalyzed regioselective dialkylation of aryl alkenes

图式22. 镍催化导向不饱和酰胺区域选择性双烷基化反应

Scheme 22. Nickel-catalyzed direction group assisted regioselective dialkylation of unsaturated amides

图式23. 镍催化导向不饱和酰胺和双亲电烷基化试剂的区域选择性双烷基化反应

Scheme 23. Nickel-catalyzed direction group assisted regioselective dialkylation of unsaturated amides with two alkyl electrophiles

图式24. 镍催化导向N-乙烯基酰胺区域选择性双烷基化反应

Scheme 24. Nickel-catalyzed direction group assisted regioselective dialkylation of N-vinyl amides

图式25. 镍催化导向苯乙烯衍生物的高效区域选择性双烷基化反应

Scheme 25. Nickel-catalyzed direction group assisted regioselective dialkylation of styrene derivatives with high efficiency

图式26. 铁-光催化剂协同催化的烯烃区域选择性双烷基化反应

Scheme 26. Iron-photo co-catalyzed regioselective dialkylation of alkenes

图式27. 镍-光催化剂协同催化的芳基烯烃区域选择性双烷基化反应

Scheme 27. Nickel-photo co-catalyzed regioselective dialkylation of aryl alkenes

图式28. 镍-光催化剂协同催化的缺电子烯烃区域选择性双烷基化反应

Scheme 28. Nickel-photo co-catalyzed regioselective dialkylation of electron-deficient alkenes

图式29. 光催化芳香烯烃和醛、三氟甲基亚磺酸钠的区域选择性双烷基化反应

Scheme 29. Photocatalyzed regioselective dialkylation of aryl alkenes with aldehydes and sodium trifluoromethanesulfinate

图式30. 光催化芳香烯烃和醛、烷基羧酸的区域选择性双烷基化反应

Scheme 30. Photocatalyzed regioselective dialkylation of aryl alkenes with aldehydes and aliphatic acids

图式31. 光催化烯烃和醛、烷基草酸单酯的区域选择性双烷基化反应

Scheme 31. Photocatalyzed regioselective dialkylation of alkenes with aldehydes and alkyl oxalate monoesters

图式32. 光催化单烯烃、共轭烯烃的区域选择性双烷基化反应

Scheme 32. Photocatalyzed regioselective dialkylation of mono-alkenes and conjugated-alkenes

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