Development of Novel Catalytic systems Using by the Cp'-P Ligand Having a Planar Chirality

我一直在研究具有Cp‘-P配体的过渡金属络合物的化学。Cp‘-P配体既有环戊二烯基衍生物，也有由合适的间隔基连接的叔膦基团。具有Cp‘-P配体的配合物有望表现出环戊二烯配合物和膦配合物的结合特性。此外，我们还可以通过我们的研究揭示CP‘-P配体的一个有趣的行为。在这个项目中，我可以发现一些有趣的结果。主要内容如下：首先，制备了几种Cp‘-P配体，并对它们的性质进行了研究。我们发现，取代基上的平面手性和立体中心的结合对于控制Rh中心上的手性是非常有效的。第二，我们获得了具有Cp‘-P配体的三条腿钢琴-凳型Rh配合物在迁移插入和迁移后插入中烷基迁移的实验证据。第三，作为在有机合成中的应用，我发展了Cp’-P Rh络合物介导的炔烃的立体和区域选择性酰甲基化反应。

I have been working on chemistry of transition metal complexes having the Cp'-P ligand. The Cp'-P ligand has both a cyclopentadienyl derivatives and a tertiary phosphine group connected by an appropriate spacer. The complexes having Cp'-P ligand are expected to show the combination character of cyclopentadienyl complexes and phosphino complexes. Addition of them, we can disclose an interesting behavior of the Cp'-P ligand through our research.In this project, I can find some interesting results obtained by using the Cp'-P ligand. Main points are shown the followings.First, I have prepared the several kinds of Cp'-P ligand and examined their characters. We can find out that the combination of planar chirality and stereogenic center on the substituent was very effective for controlling the chirality on Rh center.Second, we have obtain experimental evidence for migration of an alkyl group in migratory insertion and retro-Migratory Insertion by using the three-legged piano-stool rhodium Complex having Cp'-P Ligand.Third, as an application to organic synthesis, I have developed stereo- and regio selective acylmethylation of alkynes mediated by the Cp'-P Rh complexes.