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
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