过渡金属催化氟代烯烃参与的交叉偶联反应进展

Transition Metal-Catalyzed Cross-Coupling Reactions of Alkenyl Fluorides:Advances and Perspectives

过渡金属催化(类)卤化物和不同金属试剂的交叉偶联反应是构建不同类型碳碳键和碳杂原子键的重要方法之一。该类反应一般使用活性较高的氯、溴、碘或类卤化物作为亲电试剂,尽管C—F键的键能较强,利用过渡金属直接活化较为惰性的芳基C—F键并参与实现的交叉偶联反应已有较多报道。此外,近期的研究表明,也可以通过直接活化烯基C—F键并催化实现该类底物参与不同类型的交叉偶联反应,从而进一步拓展了交叉偶联反应的底物适用范围,并应用于具有高附加值精细化学品的选择性合成。本文围绕钯或镍催化活化单氟或者多氟烯烃等底物参与的Negishi、Suzuki-Miyaura、Kumada、Hiyama和Sonogashira等5类交叉偶联反应,通过探讨已有方法的反应机理及其适用范围,综述了该领域的研究进展并进行了展望。

As one of the most important reactions for the construction of various of carbon carbon bonds and carbon heteroatom bonds,transition metal-catalyzed cross-coupling reactions of different organic(pseudo)halides with organometallic reagents have found wide applications. Reactive organic chlorides,bromides,iodides and(pseudo)halides are often employed as electrophiles in these transformations. Despite the strong bond dissociation energy of C—F bonds,there are many reports related to the transition metal-catalyzed cross-coupling reactions of aryl fluorides by activating their C—F bonds. Furthermore,recent studies have also disclosed that alkenyl fluorides can also be employed for a variety of cross-coupling reactions via similar activation strategy,which not only broadens the scope of cross-coupling reactions,but can also be applied for the facile synthesis of highly valued fine chemicals. In this review,insightful discussions on the latest achievements of the Pd or Ni-catalyzed cross-coupling reactions(Negishi,Suzuki-Miyaura,Kumada,Hiyama and Sonogashira)of mono-and polyfluoroniated alkenes are provided. The related mechanism considerations,limitations and the opportunities of the state-of-the-art methodologies will be highlighted,and the future development is prospected.