交叉偶联反应
两个分子片段在金属催化剂的协助下结合在一起时,就会发生有机合成中的交叉偶联反应。自Heck,Negishi和Suzuki开创性的工作起,在过去30年,交叉偶联一直是催化合成化学中非常重要的一类的反应,而Heck,Negishi和Suzuki也因钯催化的交叉偶联反应获得2010年诺贝尔化学奖。交叉偶联反应作为有机合成中通用和高效的化学成键方法之一,到目前为止已经发展的非常成熟,两个分子片段可以借助合适的催化体系发生偶联。
随着交叉偶联反应使用频率的成倍增长,该领域已涵盖众多C-C键、C-N键和C-O键形成的策略,包括以下关键反应:
- Buchwald-Hartwig胺化反应是芳基(拟)卤化物和胺的交叉偶联,是各学科化学家非常常用的一类反应。
- Heck偶联是通过不饱和卤化物与烯烃发生交叉偶联反应,从而制备取代的烯烃。
- Negishi偶联是通过芳基(拟)卤化物和有机锌亲核试剂发生交叉偶联,形成C-C键。
- Sonogashira偶联是通过芳基(拟)卤化物与末端炔烃发生交叉偶联,从而合成二取代炔烃。
- Stille偶联是通过芳基(拟)卤化物和有机锡试剂发生交叉偶联,是C-C键形成的一类官能化反应,对R-基团的限制很少。
- Suzuki-Miyaura偶联是通过芳基(拟)卤化物和有机硼酸盐发生交叉偶联,是形成C-C键的常用反应。
Figure 1.Buchwald-Hartwig Amination
Figure 2.Heck Cross-Coupling Reaction
Figure 3.Negishi Cross-Coupling Reaction
Figure 4.Sonogashira Cross-Coupling Reaction
Figure 5.Stille Cross-Coupling Reaction
Figure 6.Suzuki-Miyaura Cross-Coupling Reaction
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