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Creation of Novel Environmentally Benign Low-Valent Ruthenium Catalysts

新型环保低价钌催化剂的制备

基本信息

批准号：
16205014
负责人：
MITSUDO Take-aki
金额：
$ 32.86万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
2004
资助国家：
日本
起止时间：
2004 至 2005
项目状态：
已结题

项目摘要

The creation of novel transition metal complexes which show high catalytic performance is essential for development of highly atom-economical and environmentally benign synthetic methods without the formation of byproducts. In this study, we first succeeded in preparation of novel Ru(0) complexes bearing arenes, p-quinones, and tridentate pyridyl ligands via selective displacement of either 1,3,5-cyclooctatriene (cot) or dimethyl fumarate (dmfm) ligands in Ru(η^6-cot)(η^2-dmfm)_2 (1). The stoichiometric reaction of 1 with phenol gave novel Ru(II) phenolate complexes, while the reaction of 1 with water in the presence of 1,2-bis(diphenylphosphino)ethane (dppe) gave a novel chiral Ru(0) aqua complex, Ru(η^2-dppe)(η^2-dmfm)_2(H_2O) (2). The structures of all novel complexes were clearly determined by X-ray crystallography. Optical resolution of rac-2 was successfully performed by HPLC equipped with a chiral column.In addition, we have developed the following novel catalytic reactions characteristic to ruthenium ; 1)formal [4+2] cycloaddition of alkynes with electron-deficient alkenes to cyclohexenedicarboxylates via isomerization of alkynes and successive Diels-Alder reaction, 2)[2+2+2] cocyclotrimerization of three different alkynes (dimethyl acetylenedicarboxylate, 1-decyne and 3-hexyne), 3)regio- and stereoselective linear codimerization of 2-norbornenes with acrylic compounds, 4)synthesis of 2-alkylidenetetrahydrofurans by codimerization of dihydrofurans with α,β-unsaturated esters. All these ruthenium-catalyzed reactions offered the synthetic methods for novel functional monomers with high atom-efficiency.

创造新型的过渡金属配合物，表现出高催化性能是必不可少的高度原子经济和环境友好的合成方法的发展，而不会形成副产物。在本研究中，我们首次成功地通过选择性取代Ru（η^6-cot）（η^2-dmfm）_2（1）中的1，3，5-环辛三烯（cot）或富马酸二甲酯（dmfm）配体，制备了含芳烃、对醌和三齿吡啶配体的新型Ru（0）配合物。1与苯酚的化学计量反应得到了新的Ru（II）苯酚配合物，而1与水在1，2-二（二苯基膦基）乙烷（dppe）存在下的反应得到了新的手性Ru（0）水配合物Ru（η^2-dppe）（η ^2-dmfm）_2（H_2O）（2）。所有新的配合物的结构都通过X射线晶体学明确确定。此外，我们还开发了以下钌催化的新反应：1）通过炔的异构化和随后的Diels-Alder反应，炔与缺电子烯烃形成环己烯二羧酸酯的形式[4+2]环加成，2）三种不同炔的[2+2+2]共环三聚反应（乙炔二羧酸二甲酯，1-癸炔和3-己炔），3）2-己烯与丙烯酸类化合物的区域和立体选择性线性共聚，4）二氢呋喃与α，β-不饱和酯共聚合合成2-亚烷基四氢呋喃。这些反应为高原子效率的新型功能单体的合成提供了新的途径。