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.

新型过渡金属络合物的创建表现出高催化性能对于发展高度原子经济和环境良性合成方法至关重要。在这项研究中，我们首先通过选择性置换1,3,5-循环替代，以准备新的Ru（0）络合物轴承谱，p- Quinones，Tridentate吡啶基配体和马来酰亚胺。（η^2-二甲基富马酸）_2（1）。 In sharp contrast, a similar Ru (0) complex, Ru (η^4-1,5-cyclooctatriene) (η^6-1,3,5-cyclooctatriene) (2) smoothly reacted with maleimides to give novel divalent ruthenacyclopentane complexes (3) via oxide cyclization of a cot ligand and maleimides on the ruthenium, which may realize the development of novel过渡金属催化剂[6+2]的共钙化反应。基于上述化学计量反应，在本研究中已经开发了使用环境良性的氟芬氏菌和铑催化剂来构建各种环化合物的新方法。 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 electronic-deficiency alkenes via C-C bond cleavage/dehydrogenation, and 4) selective codimerization and cotrimerization of different alkenes, as well as selective trimerization of ethylene, via ruthenacycle中间人。所有反应都以高原子效率进行，并提供功能性单体而没有副产品的形成。

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）

ルテニウム錯体触媒を用いるアルキンの高位置および立体選択的チオアリル化反応

使用钌配合物催化剂对炔烃进行高度区域和立体选择性硫代烯丙基化

DOI：
发表时间：
2007
期刊：
影响因子：
0
作者：
野村琴広;板垣浩司(著者分担);福田崇
通讯作者：
福田崇

Novel Synthesis of Ketene Dithioacetals via Ruthenium-catalyzed 1,1Addition of Organic Disulfides to Terminal Alkynes

通过钌催化有机二硫化物与末端炔烃 1,1 加成新合成乙烯酮二硫缩醛

DOI：
发表时间：
2008
期刊：
影响因子：
0
作者：
Takashi Fukuda. Kenji Wada;Take-aki Mitsudo;Teruyuki Kondo
通讯作者：
Teruyuki 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

DOI：
发表时间：
2006
期刊：
Organometallics 25(12)
影响因子：
0
作者：
K. Nakabayashi;S. Ohkoshi;Yasuyuki Ura
通讯作者：
Yasuyuki Ura

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] Cycloaddition of 1,3,5-Trienes and Alkynes

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] 1,3,5-三烯和炔烃的环加成反应