Synthesis of Non-prophyrine Complexes and their synthetic application

合成了非卟啉过渡金属配合物作为基本设计。它们有一个吡啶骨架和两个恶唑啉基团。通过单晶X-射线分析确定了它们的结构。在络合物中，舌状部分与金属中心结合强烈。合成了含卤素、一氧化碳或乙烯的配合物。考察了它们的络合物的氧化活性，表明它们对烯烃的非选择性氧化。报道了在卟啉体系中，吡啶-恶唑啉、非卟啉体系与重氮乙酸酯和环丙烯衍生物作为卡宾受体。我们发现了一种立体专一性的卡宾转移反应，以获得高的反式选择性，超过95%。我们可以定义一个卡宾从络合物转移到烯烃的机理。用核磁共振波谱观察到卡宾单元=CH-的特征信号。总体而言，卟啉类化合物不容易合成。然而，我们设计的含Ru金属的吡啶-恶唑啉配体对氧化和环丙烷化的作用非常相似。在下一步，我们希望展示它们的络合物的高催化活性。

Non-porphyrine transition-metal complexesas as a basic design were syntheized. They have a pyridine skeleton and two oxazoline groups. Their structures were determined by singl crystal X-ray analysis. In the complexes, the lingad part is combining to the metal center strongly. The complexes having halogens, CO,or ethylene were also synthesized. The activity of oxidation withtheir complexes were examined to show non-selective oxidation of olefins. Aspreported in porphyrine system, the pyridine-oxazoline, non-porphyrine sytemact as carbene acceptor with diazoacetates and cyclopropene derivative. We discoved a stereospecific carbene transferreaction to stirene to give high trans selectivity, more than 95%. We can define a mechanism of carbene transfer from the complexes to olefins. The characteristic signals for the carbene unit=CH-were observed by NMR spectroscopy. In general, porphyrine systems were not easy to synthesis. However, our desinged pyridine-oxazoline ligans with ruthenium metal act very silimarly for oxidation and cyclopropanation. In next steps, we are expecting to demonstrate high catalytic activity of their complexes.