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

当两个不饱和化合物偶联在锆新世（II）上时，高收率地形成五元锆环。锆环的碳-碳键裂解后与另一不饱和化合物的二次偶联形成了不同类型的锆环。特别是当两个不饱和化合物的直接偶联比较困难时，我们所开发的方法是非常有用的。在这个项目中，我们进一步开发了有用的反应。含2个卤素的吡啶类化合物在CuCl存在下与锆环戊二烯反应，在C2和C3碳上形成新的2个碳-碳键。喹啉衍生物以高收率形成。当使用3,4-二卤吡啶时，以类似的方式得到异喹啉衍生物。对于这些反应，可以使用各种取代基。无论是单环的锆环戊二烯，还是双环的锆环戊二烯，反应都没有问题。

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.