无过渡金属催化的Suzuki-Type交叉偶联反应研究进展

doi:10.6023/cjoc202208008

摘要/Abstract

过渡金属催化的Suzuki交叉偶联反应是构建碳碳键最高效和最广泛的方法之一, 其广泛的研究极大地推动了合成化学的发展. 当前Suzuki交叉偶联反应主要依赖于贵金属钯催化体系, 然而, 金属钯储量低、价格昂贵及高毒性等弊端已经严重地限制了其在现代合成中的发展. 在过去二十年时间, 无金属催化的Suzuki-Type交叉偶联反应受到了广泛的关注, 许多新型高效的反应体系被开发报道. 总结了近二十年无金属催化的Suzuki-Type交叉偶联反应的研究进展, 主要涉及的反应类型包括碱、金属有机试剂和有机小分子促进的反应, 并对相关的反应机理进行了阐述.

关键词: 无金属催化, Suzuki交叉偶联, 有机合成, 碱促进, 偶联反应

Transition metal catalyzed Suzuki coupling reaction serves as one of the most versatile and widespread methods for the C-C bonds formation, which greatly promotes the development of synthetic chemistry. Currently, the Suzuki coupling reactions heavily rely on noble palladium-catalyzed system. However, the high cost, toxicity and low reserves of palladium have become the main obstacles for their development in organic synthesis. Over the past two decades, metal-free catalyzed Suzuki-Type cross coupling reactions earned extensive concern, and a large number of efficient and new reaction systems have been reported. In this review, the recent progresses of metal-free catalyzed Suzuki-Type cross coupling reactions are summarized, mainly including bases, organometallic reagents and organic molecules promoted reactions. In addition, the mechanism of reaction is also discussed in this review.

Key words: metal-free catalysis, Suzuki cross-coupling, organic synthesis, base promoting, coupling reaction

引用此文

马彪, 章淼淼, 李占宇, 彭进松, 陈春霞. 无过渡金属催化的Suzuki-Type交叉偶联反应研究进展[J]. 有机化学, 2023, 43(2): 455-470.

Biao Ma, Miaomiao Zhang, Zhanyu Li, Jinsong Peng, Chunxia Chen. Recent Advance of Transition Metal-Free Catalyzed Suzuki-Type Cross Coupling Reaction[J]. Chinese Journal of Organic Chemistry, 2023, 43(2): 455-470.

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图/表 36

图式1. 烯丙基溴与芳基硼酸的Suzuki-Type交叉偶联反应

Scheme 1. Suzuki-Type cross coupling reaction of allyl bromides with aryl boroic acids

图式2. 磺酸酯与芳基硼酸的Suzuki-Type交叉偶联反应

Scheme 2. Suzuki-Type cross coupling reaction of sulfonate with aryl boroic acids

图式3. 磺酸酯与芳基硼酸偶联可能的机理

Scheme 3. Possible mechanism for coupling sulfonate with boroic acids

图式4. 烯丙基溴与芳基硼酸的Suzuki-Type交叉偶联反应

Scheme 4. Suzuki-Type cross coupling reaction between allyl bromines and aryl boroic acids

图式5. 炔丙基溴与芳基硼酸的Suzuki-Type交叉偶联反应

Scheme 5. Suzuki-Type cross coupling reaction between propargyl bromines and aryl boric acids

图式6. 两种类型的偶联反应

Scheme 6. Two types of coupling reactions

图式7. 苄基卤化物和芳基硼酸的Suzuki-Type交叉偶联反应

Scheme 7. Suzuki-Type cross coupling reaction of benzyl halides and aryl boroic acids

图式8. 苄基卤化物与芳基硼酸偶联可能的机理

Scheme 8. Possible mechanism for coupling benzyl halides and aryl boroic acids

图式9. 烷基卤化物或类卤化物与烯基硼酸的Suzuki-Type交叉偶联反应

Scheme 9. Suzuki-Type cross coupling reaction of alkyl halides or pseudohalides with alkenyl boric acids

图式10. 烷基卤化物或类卤化物与烯基硼酸偶联相关机理验证实验

Scheme 10. Mechanistic verification experiments related to the coupling of alkyl halides or pseudohalides with alkenyl boric acids

图式11. 烯基硼酸与sp3亲电试剂的Suzuki-Type交叉偶联反应

Scheme 11. Suzuki-Type cross coupling reaction coupling of alkenyl boronic acids with sp3 electrophiles

图式12. 烯基硼酸与sp3亲电试剂偶联可能的机理

Scheme 12. Possible mechanism for coupling alkenyl boronic acids with sp3 electrophiles

图式13. 苄基类卤化物与芳基硼酸的Suzuki-Type交叉偶联反应

Scheme 13. Suzuki-Type cross coupling reaction of benzyl halides with aryl boronic acids

图式14. 苄基类卤化物与芳基硼酸偶联可能的机理

Scheme 14. Possible mechanism for coupling benzyl halides with aryl boronic acids

图式15. 苯甲酰氯和芳基硼酸的Suzuki-Type交叉偶联反应

Scheme 15. Suzuki-Type cross coupling reaction of benzoyl chlorides and aryl boronic acids

图式16. 双硼化合物与卤代烃的Suzuki-Type交叉偶联反应

Scheme 16. Suzuki-Type cross coupling reaction of deborylatives with halogenated hydrocarbons

图式17. 双硼化合物与卤代烃偶联相关机理验证实验

Scheme 17. Mechanistic verification experiments related to the coupling of deborylatives with halogenated hydrocarbons

图式18. 叔苄基硼酸酯与亲电试剂的Suzuki-Type交叉偶联反应

Scheme 18. Suzuki-Type cross coupling reaction of tert-benzyl borate esters with electrophilic reagents

图式19. 叔苄基硼酸酯与亲电试剂偶联相关机理验证实验

Scheme 19. Mechanistic verification experiments related to the coupling of tert-benzyl boronic acid esters with electrophilic reagents

图式20. 叔苄基硼酸酯与亲电试剂偶联可能的机理

Scheme 20. Possible mechanism for coupling tert-benzyl boronic acid esters with electrophilic reagents

图式21. 富电子芳烃与硼酸酯的Suzuki-Type交叉偶联反应

Scheme 21. Suzuki-Type cross coupling reaction of electron-rich aromatics with borate esters

图式22. 富电子芳烃与硼酸酯偶联可能的机理

Scheme 22. Possible mechanism for coupling electron-rich aromatics with borate esters

图式23. 芳基硼酸的纯度对反应的影响

Scheme 23. Effect of the purity of arylboronic acid on the reaction

图式24. 阐明芳基硼酸和二乙基锌混合后产生的物种

Scheme 24. Elucidation of the species generated upon mixing an arylboronic acid and diethylzinc

图式25. 芳基硼酸酐与碘苯的Suzuki-Type偶联反应

Scheme 25. Suzuki-Type cross coupling reaction between aryl boric anhydrides and iodobenzenes

图式26. 芳基硼酸酐与碘苯偶联可能的机理

Scheme 26. Possible mechanism for coupling arylboronic anhydride with iodobenzene

图式27. 硼酸酯的立体选择性的单氟和二氟甲基化

Scheme 27. Stereospecific mono- and difluoromethylation of boronic esters

图式28. 苄基卤化物与芳基硼酸的Suzuki-Type偶联反应

Scheme 28. Suzuki-Type cross coupling reaction of benzyl halides with aryl boronic acids

图式29. 苄基卤化物与芳基硼酸偶联可能的机理

Scheme 29. Possible mechanism for coupling benzyl halides with aryl boronic acids

图式30. 有机小分子硫催化剂的失活

Scheme 30. Deactivation of organic small molecule sulfur catalysts

图式31. 有机小分子硫催化的Suzuki-Type交叉偶联反应

Scheme 31. Suzuki-Type cross coupling reaction catalyzed by organic small molecule sulfur

图式32. 芳基硼酸与芳基卤化物的Suzuki-Type偶联反应

Scheme 32. Suzuki-Type cross coupling reaction between aryl boronic acids and aryl halides

图式33. 小分子硫促进Suzuki-Type偶联可能的机理

Scheme 33. Possible mechanism of Suzuki-Type coupling facilitated by small molecule sulfur

图式34. 有机膦催化的Suzuki-Type交叉偶联反应

Scheme 34. Suzuki-Type cross coupling reaction catalyzed by organophosphorus

图式35. 光诱导的Suzuki-Type交叉偶联反应

Scheme 35. Light-induced Suzuki-Type cross-coupling reaction

图式36. 光诱导Suzuki-Type偶联可能的机理

Scheme 36. Possible mechanism of light-induced Suzuki-Type coupling

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