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Development of Methods for Novel Construction of Ring Compounds by Environmentally Benign Transition Metal Catalysts

环境友好的过渡金属催化剂构建环状化合物的新方法的发展

基本信息

批准号：
18350050
负责人：
KONDO Teruyuki
金额：
$ 10.52万
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：
2006
资助国家：
日本
起止时间：
2006 至 2007
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. In this study, we first succeeded in preparation of novel Ru (0) complexes bearing arenes, p-quinones, tridentate pyridyl ligands, and maleimides via selective displacement of either1,3,5-cyclooctatriene (cot) or dimethyl fumarate (dmfm) ligands in Ru (η^6-1,3,5-cyclooctatriene) (η^2-dimethyl fumarate)_2 (1). In sharp contrast, a similar Ru (0) complex, Ru (η^4-1,5-cyclooctadiene) (η^6-1,3,5-cyclooctatriene) (2) smoothly reacted with maleimides to give novel divalent ruthenacyclopentane complexes (3) via oxidative cyclization of a cot ligand and maleimides on the ruthenium, which may realize the development of novel transition-metal catalyzed [6+2] cocyclization reaction.Based on the above described stoichiometric reactions, novel methods for construction of various ring compounds using environmentally benign ruthenium and rhodium catalysts have been developed in this study. Representative examples include 1) first ruthenium-catalyzed [2+2+1] cocyclization of isocyanates, alkynes, and carbon monoxide enables the rapid synthesis of polysubstituted maleimides, 2) rhodium-catalyzed cyclocotrimerization of isocyanates and alkynes leading to the selective formation of 2-pyridones and pyrimicline-2,4-diones by controlling the molar ratio of isocyanates and alkynes, 3) rhodium-catalyzed direct synthesis of substituted phenols from cyclobutenones and electron-deficient alkenes via C-C bond cleavage/dehydrogenation, and 4) selective codimerization and cotrimerization of different alkenes, as well as selective trimerization of ethylene, via ruthenacyclic intermediates. All reactions proceed with high atom-efficiency and give functional monomers without the formation of byproducts.

开发具有高催化性能的新型过渡金属配合物，对于开发原子经济性高、环境友好的合成方法具有重要意义。在本研究中，我们首次通过选择性置换Ru(η^6-1，3，5-环辛三烯)(η^2-二甲基富马酸二甲酯)_2(1)中的1，3，5-环辛三烯(COT)或富马酸二甲酯(DMFM)配体，成功地合成了含芳烃、对苯二酚、三齿吡啶和马来酰亚胺的新型Ru(0)配合物。与之形成鲜明对比的是，类似的Ru(0)配合物Ru(η^4-1，5-环辛二烯)(η^6-1，3，5-环辛三烯)(2)与马来酰亚胺通过钴配体和马来酰亚胺在Ru上的氧化环化反应得到了新型的二价环戊烷配合物(3)，这可能实现新型过渡金属催化的[6+2]共环反应。具有代表性的例子包括：1)1)Ru催化的异氰酸酯、炔烃和一氧化碳的[2+2+1]共环化反应使多取代马来酰亚胺的快速合成成为可能；2)Ru催化的异氰酸酯和炔烃的环共三聚反应通过控制异氰酸酯和烯烃的摩尔比选择性地生成2-吡啶酮和2，4-吡咪-2，4-二酮；3)通过C-C键裂解/脱氢由环丁烯和缺电子的烯烃直接合成取代酚；4)不同烯烃的选择性共二聚和共聚合，以及通过苯环中间体选择性的乙烯三聚反应。所有反应都以高原子效率进行，并且得到功能单体，没有副产物的形成。

项目成果

期刊论文数量（0）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Synthesis and Characterization of a Novel (μ_3-oxo)tetraruthenium Cluster

新型(μ_3-oxo)四钌簇的合成与表征

DOI：
发表时间：
2007
期刊：
J. Organomet. Chem 692(1-3)
影响因子：
0
作者：
宮部季隆;長谷陽子;飯田拡基;前田勝浩;八島栄次;Takeshi Okumura,;Takeshi Okumura;Takeshi Okumura;Hidekazu Arii;Yuji Kajita;I.Kondo
通讯作者：
I.Kondo

Formation of Divalent Ruthenacycles via Oxidative Cyclization of 1, 3, 5-Cyclooctatriene with Maleic Anhydride or Maleimides : An Intermediate for the Transition Metal-Mediated [6+2] Cyclo-addition of 1, 3, 5-Trienes and Alkenes

通过 1, 3, 5-环辛三烯与马来酸酐或马来酰亚胺的氧化环化形成二价钌环：过渡金属介导的中间体 [6 2] 1, 3, 5-三烯和烯烃的环加成