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Synthetic Reactions by Using Bimetallic Complexes

使用双金属配合物的合成反应

基本信息

批准号：
16205012
负责人：
NARASAKA Koichi
金额：
$ 25.88万
依托单位：
The University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
2004
资助国家：
日本
起止时间：
2004 至 2006
项目状态：
已结题

项目摘要

In catalytic synthetic reactions, monometallic complexes have been widely used, while bimetallic complexes rarely used in practical synthesis. Precise design of bimetallic complexes is expected to realize unique chemical transformations, in which multi metal centers take part in the reactions collaboratively. In this research, homo and hetero bimetallic complexes were prepared and their catalytic activities were studied to realize organic transformations.1)Phosphido-bridged rhodium-tungsten carbonyl complexes were prepared, expecting catalytic activity of Rh(I) with the assistance by the W part as a CO donor and/or Lewis acidity. A Rh-W bimetallic complex exhibited high catalytic activity in the hydroformylation of monosubstituted alkenes even under less than 0.04 atm partial pressure of CO, with a wide functional group selectivity. A oxygen- or sulfur-bridged bimetallic were prepared and their structures were studied by X-ray crystallographic analysis. The oxygen-bridged complex exhib … More ited a unique character in the hydrogenation of alkenes; that is, outer alkenes are smoothly hydrogenated, while the ligand alkene (cyclooctadiene) is not.2)Vinyl nitrene-metal complexes, the property of which is not fully clarified yet, was found to be easily generated from azirines and vinyl azides, particularly by the treatment with rhodium(II) bimetallic complexes and copper(II) complexes. Indoles and pyrroles were prepared catalytically by aromatic C-H amination and addition reaction of active methylene compounds to the vinyl nitrene-metal complexes.3)During the course of the study on the oxidative generation of β-keto radicals from cyclopropanols, silver(I) complexes are found to show high activity. Catalytic process was accomplished by adding adequate reoxidation reagent and applied for the intramolecular ring expansion. The catalytic generation of β-keto radicals was so powerful to construct fused rings that synthesis of (-)-sordarin was achieved by using the catalysis as the key step. Less

在催化合成反应中，单金属配合物得到了广泛的应用，而单金属配合物在实际合成中应用较少。通过对配合物的精确设计，可以实现多金属中心协同参与的独特化学反应。本研究制备了均、杂铑配合物，并研究了它们的催化活性。1）制备了磷桥铑钨羰基配合物，期望在W部分作为CO供体和/或刘易斯酸性的辅助下，Rh（I）具有催化活性。铑钨配合物在CO分压低于0.04 atm时对单取代烯烃的加氢反应仍表现出较高的催化活性，并具有较宽的官能团选择性。制备了氧桥或硫桥的双金属配合物，并通过X射线晶体学分析研究了它们的结构。氧桥络合物 ...更多信息 2）氮杂环丙烷和乙烯叠氮化合物容易生成乙烯基氮烯-金属配合物，其性质尚未完全阐明，特别是通过铑（II）络合物和铜（II）络合物的处理。通过芳香族C-H胺化反应和活性亚甲基化合物与乙烯基氮烯-金属配合物的加成反应，催化合成了吲哚和吡咯。3）在环丙醇氧化生成β-酮自由基的研究中，发现银（I）配合物具有较高的催化活性。催化过程通过加入适量的再氧化剂完成，并用于分子内扩环。β-酮自由基的催化生成对稠环的形成具有很强的催化作用，因此利用β-酮自由基的催化作用合成了（-）-山梨糖醇苷。少