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Creation of Innovative and Environmentally Benign Methods for Catalytic Construction of Ring Compounds via Reactive Metallacyclic Intermediates

创建通过反应性金属环中间体催化构建环状化合物的创新且环保的方法

基本信息

批准号：
20350048
负责人：
KONDO Teruyuki
金额：
$ 12.65万
依托单位：
Kyoto University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2008
资助国家：
日本
起止时间：
2008 至 2010
项目状态：
已结题

项目摘要

For the continuing prosperity of human society in the 21st century, it is essential to construct environmentally benign catalytic processes without byproducts and waste, directed toward organic synthesis. In the Scientific Research B, novel rhodium-catalyzed cross-coupling and cycloaddition reactions of ketenes with alkenes or alkynes have been developed, leading to efficient methods for construction of cyclopropanes, 2-pyridones, pyrimidine-2,4-diones, and furans, which constitute new and functional monomers and materials. On the other hand, we have made an important contribution to ruthenium chemistry by developing a lot of novel ruthenium-catalyzed reactions as well as creation of novel Ru (0) and Ru (II) monomers and clusters. Recently, we have succeeded in development of codimerization and cotrimerization reactions of different alkenes, and in the Scientific Research B, we found that our original ruthenium(0) complex, Ru(η^6-cot)(η^2-dmfm)_2 [cot =1,3,5-cyclooctatriene, dmfm = dimethyl fumarate], showed high catalytic activity for selective trimerization of ethylene to isohexenes. It seems that the reaction proceeds via normal and successive insertion of ethylene into an alkyl-ruthenium bond. However, the present reaction proceeded via ruthenacyclopentanes as a key intermediate, which was confirmed by the formation of unusual isohexenes (a branched cotrimer) in place of normal 1-hexene (a linear cotrimer) as well as deuterium-labeled experiments. Accordingly, the reactions developed in this Scientific Research B are all atom-economical and environmentally benign processes, which offer innovative methods for construction of ring compounds via an efficient formation of metallacyclic intermediates. As a result, this research contributes significantly to green sustainable chemistry (GSC) for organic synthesis in the 21st century.

为了人类社会在21世纪世纪的持续繁荣，必须构建环境友好的无副产物和废物的催化过程，直接用于有机合成。在科学研究B中，开发了新的铑催化的烯酮与烯烃或炔的交叉偶联和环加成反应，从而有效地构建了环丙烷、2-吡啶酮、嘧啶-2，4-二酮和呋喃，这些构成了新的功能单体和材料。另一方面，我们通过开发许多新颖的钌催化反应以及产生新颖的Ru（0）和Ru（II）单体和簇合物，对钌化学做出了重要贡献。近年来，我们成功地开发了不同烯烃的共聚合和共三聚反应，并在科研B中发现我们的钌（0）配合物Ru（η^6-cot）（η^2-dmfm）_2 [cot = 1，3，5-cycloocttriene，dmfm = dimethyl fumarate]对乙烯选择性三聚制异己烯具有很高的催化活性。反应似乎是通过乙烯正常和连续插入烷基-钌键进行的。然而，本反应通过环己烯环戊烷作为关键中间体进行，这通过形成不寻常的异己烯（支链共三聚体）代替正常的1-己烯（线性共三聚体）以及氘标记的实验来证实。因此，在本科学研究B中开发的反应都是原子经济和环境友好的过程，其提供了通过有效形成金属环中间体来构建环化合物的创新方法。因此，本研究对21世纪世纪有机合成的绿色可持续发展具有重要意义。