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.

对于21世纪人类社会的持续繁荣，必须在没有副产品和废物的情况下建立环境良性的催化过程，该过程针对有机综合。在科学研究B中，已经开发了新型的矿矿催化交叉耦合和环载反应，并开发了烷烃或炔烃的反应，从而有效地构成了环丙酮，2-吡啶酮，嘧啶-2,4-二酮和属于新的和材料和功能性怪物和材料的有效方法。另一方面，我们通过开发许多新型的氟芬催化反应以及创造新颖的RU（0）和Ru（II）单体和簇来为四归化学做出了重要贡献。 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], shown high catalytic activity for selective将乙烯对等异己烯的三烯化。该反应似乎是通过将乙烯插入醇正义键的正常和成功插入的。然而，本反应通过鲁思烯酰基戊烷作为关键中间体进行，通过形成异常的异己烯（分支棉），代替正常的1-己烯（线性辅助膜）以及氘标记的实验来证实。彼此之间，这项科学研究B中发展的反应都是原子经济和环境良性的过程，它们通过有效地形成冶金中间体，为构建环化合物的创新方法提供了创新的方法。结果，这项研究对21世纪有机合成造成了绿色可持续化学（GSC）的贡献。