Suzuki-Miyaura偶联反应机理研究进展

doi:10.6023/cjoc202103040

摘要/Abstract

钯催化的Suzuki-Miyaura偶联反应是目前应用最广泛的合成方法之一. 它以卤化物和有机硼化物作为原料, 可以高效地构建碳碳键. 有机硼化物不仅具有转金属活性, 而且与其它主族金属有机试剂相比具有化学性质稳定、安全低毒及合成方法多样的特点. Suzuki-Miyaura偶联反应具有反应条件温和、转化高效和底物普适性广等突出优势, 是合成化学研究者构建C—C键的优先选择, 而且它已在工业合成领域中被广泛应用. Suzuki-Miyaura偶联反应的快速发展与广泛应用离不开机理研究的进步. 近三十年里, 诸多研究者设计并开展了细致的机理研究, 揭示了Suzuki-Miyaura偶联反应中更多的反应规律. Suzuki-Miyaura偶联反应的催化循环由氧化加成、转金属与还原消除三个过程组成, 依次综述了各过程相关机理的研究进展, 并在最后简单介绍了无过渡金属参与和无碱参与的Suzuki-Miyaura偶联反应.

关键词: Suzuki-Miyaura偶联反应, 机理研究, 氧化加成, 转金属, 预转金属, 还原消除

During the past several decades, Suzuki-Miyaura cross-coupling reaction has emerged and flourished as one of the most remarkable and practical methods to construct C—C bond. The substrates, organoboronic compounds, are usually more stable, less toxic and easier to obtain compared with other metal or metalloid alternatives. Suzuki-Miyaura cross-coupling reaction possesses extraordinary merits of demonstrated efficiency, broad functional group compatibility and mild reaction conditions. It has been the premier method to construct C—C bond for organic synthetic chemists and has been widely applied in the industrial syntheses. The rapid development of Suzuki-Miyaura cross-coupling reaction is accompanied with the progress of mechanism studies. It is well accepted that the catalytic cycle of Suzuki-Miyaura cross-coupling reaction contains three main steps: oxidative addition of organic halides to Pd catalysts, transmetalation between oxidative addition intermediates and organoboronic compounds, and reductive elimination from transmetalation intermediates to form C—C bond along with regenerating Pd catalysts. However, these three main steps can be influenced by diverse reaction conditions, and different reaction pathways may occur within each single step. Furthermore, beyond the oxidative addition and transmetalation intermediates, other transient but crucial intermediates may exist. To figure out these issues and discover more insights into Suzuki- Miyaura cross-coupling reaction, numerous researchers have designed and conducted systematic investigations. Herein, the recent progress of mechanism studies is summarized and discussed. The steps of oxidative addition, transmetalation and reductive elimination are discussed in detail. Moreover, a brief introduction of transition-metal-free and base-free Suzuki- Miyaura cross-coupling reactions which show more possibilities of the reaction mechanism is given. Besides summary of precedent research works, our opinions about future development of the mechanism studies are also given. Although breakthroughs have been made in the mechanism studies, further investigations are needed to bring comprehensive knowledge of this reaction and help us further optimize the reaction conditions.

Key words: Suzuki-Miyaura cross-coupling reaction, mechanism study, oxidative addition, transmetalation, pre-transmetala- tion, reductive elimination

引用此文

张雷, 杨晨, 郭雪峰, 莫凡洋. Suzuki-Miyaura偶联反应机理研究进展[J]. 有机化学, 2021, 41(9): 3492-3510.

Lei Zhang, Chen Yang, Xuefeng Guo, Fanyang Mo. Research Progress of Suzuki-Miyaura Cross-Coupling Reaction Mechanism[J]. Chinese Journal of Organic Chemistry, 2021, 41(9): 3492-3510.

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图/表 29

图式1. Suzuki-Miyaura偶联反应催化循环

Scheme 1. Catalytic cycle of Suzuki-Miyaura cross-coupling reaction

图式2. 极性试剂的氧化加成机理(金属M的角标表示价态)

Scheme 2. Oxidative addition mechanisms of polar reagents (superscript of M meaning valence states)

图式3. 烷基碘化物与有机硼烷的Suzuki-Miyaura偶联反应

Scheme 3. Suzuki-Miyaura cross-coupling reaction of alkyl iodides and organoboranes

图式4. 芳基硼酸的二氟烷基化反应

Scheme 4. Difluoroalkylation of aryl boronic acids

图式5. Pd(Ⅳ)氧化加成中间体的合成

Scheme 5. Synthesis of Pd(Ⅳ) oxidative addition intermediates

图式6. 降冰片烯参与的Pd(Ⅱ)/Pd(Ⅳ)循环

Scheme 6. Norbornene involved Pd(Ⅱ)/Pd(Ⅳ) cycle

图式7. Pd(Ⅳ)中间体参与的消旋化偶联反应

Scheme 7. Pd(Ⅳ) intermediates involved racemized cross-coupling

图式8. Iwasa及其合作者关于钯螯合物催化剂的报道

Scheme 8. Report of Pd catalysts containing pincer ligand from Iwasa and co-workers

图式9. Frech及其合作者关于钯螯合物催化剂的报道

Scheme 9. Report of Pd catalysts containing pincer ligand from Frech and co-workers

图式10. 非常规氮杂卡宾-钯配合物在Suzuki-Miyaura偶联反应中的应用

Scheme 10. Application of abnormal NHC-Pd complexes in Suzuki-Miyaura cross-coupling reactions

图式11. 转金属过程

Scheme 11. Transmetalation process

图12. 关于预转金属中间体的早期探索

Scheme 12. Preliminary investigation of pre-transmetalation intermediates

图式13. 利用核磁检测预转金属中间体的尝试

Scheme 13. Attempts of detecting pre-transmetalation intermediates via NMR

图式14. 预转金属中间体的合成

Scheme 14. Synthesis of pre-transmetalation intermediates

图式15. 转金属过程的路线A与路线B

Scheme 15. Path A and path B of transmetalation

Entry	Reaction time/h	Reactant	Product	Yield/%
1	1	Bu-9-BBN	Ph-Bu	40
1	1	Hex-9-BBN	Ph-Hex	48
2	12	Hex-9-BBN	Ph-Hex	86
2	12	Bu-OBBN	Ph-Bu	0
3	12	Bu-9-BBN	Ph-Bu	84
3	12	Hex-OBBN	Ph-Hex	0
4	12	Bu-OBBN	Ph-Bu	44
4	12	Hex-OBBN	Ph-Hex	49

表1. R-9-BBN与R-OBBD的活性比较

Table 1. Comparison of R-9-BBN and R-OBBD in reaction activity

图式16. R-9-BBN与R-OBBD参与反应的机理

Scheme 16. Mechanism of reactions related to R-9-BBN and R-OBBD

图式17. 结合电化学技术的反应路线研究

Scheme 17. Distinction of reaction pathways facilitated by electrochemical techniques

图式18. 氟离子及碱金属阳离子对转金属过程的影响

Scheme 18. Influence of fluorinion and alkali metal cation on transmetalation

图式19. 化学计量的反应动力学研究

Scheme 19. Kinetic studies of stoichiometric reactions

图式20. 模型反应的动力学研究

Scheme 20. Kinetic studies of model reactions

图式21. 转金属过程中的活化参数与膦配体对反应速率的影响

Scheme 21. Activation parameters of transmetalation process and effect of phosphine ligands on reaction rate

图式22. 转金属过程中的自催化

Scheme 22. Autocatalysis in transmetalation

图式23. 芳基硼酸酯对转金属过程的影响

Scheme 23. Influence of boronic esters on transmetalation process

图24. 反式二芳基钯配合物的还原消除

Scheme 24. Reductive elimination of trans-diarylpalladium complexes

图式25. 顺式二芳基钯配合物的还原消除

Scheme 25. Reductive elimination of cis-diarylpalladium complexes

图式26. 负离子对还原消除的影响

Scheme 26. Influence of anions on reductive elimination

图式27. 无过渡金属参与的Suzuki-Miyaura偶联反应

Scheme 27. Transition-metal-free Suzuki-Miyaura cross-coupling reactions

图式28. 无碱参与的Suzuki-Miyaura偶联反应

Scheme 28. Base-free Suzuki-Miyaura cross-coupling reactions

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