Development and Application of Coupling Reactions via Carbon-Carbon Bond Ceavage

当两个不饱和化合物偶联到二茂锆（II）上时，可以高产率地形成五元锆杂环。碳-碳键断裂的锆杂环，然后与另一个不饱和化合物的第二次耦合提供了各种类型的锆杂环。特别是，当两个不饱和化合物的直接偶联是困难的，我们开发的方法是非常有用的。在这个项目中，我们开发了更多有用的反应。在CuCl存在下，C2和C3碳上带有两个卤素的吡啶与锆并环戊二烯反应，在C2和C3碳上形成新的两个碳-碳键。喹啉衍生物以高产率形成。当使用3，4-二卤代吡啶时，以类似的方式获得异喹啉衍生物。对于这些反应，可以使用各种取代基。不仅单环的锆并环戊二烯，而且双环的锆并环戊二烯也没有任何问题地反应。

When two of unsaturated compounds couple on zirconocene (II), five-membered zirconacycles were formed in high yields. Carbon-carbon bond cleavage of the zirconacycles followed by the second coupling with another unsaturated compounds afforded various types of zirconacycles. In particular, when the direct coupling of two unsaturated compounds is difficult, our method developed is very useful. In this project we developed further useful reactions. Pyridines with two halogens at C2 and C3 carbons reacted with zirconacyclopentadienes in the presence of CuCl, new two carbon-carbon bonds were formed at C2 and C3 carbons. Quinoline derivatives were formed in high yields. When 3,4-dihalopyridines were used, isoquinoline derivatives were obtained in a similar manner. For these reactions, various substituents could be used. Not only monocyclic zirconacyclopentadienes, but also bicyclic zirconacyclopentadienes reacted without any problems.