Synthesis of Non-prophyrine Complexes and their synthetic application

非卟啉配合物的合成及其合成应用

• 批准号: 06651004
• 负责人: NISHIYAMA Hisao
• 金额: $ 1.41万
• 依托单位: Toyohashi University of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1994
• 资助国家: 日本
• 起止时间: 1994 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-06651004/
• 关键词: pyridine; complex; carbene; oxidation; ruthenium; cyclopropanation; diazocompounds; 錯体; カルベン; ビピリジン; エポキシ化

Non-porphyrine transition-metal complexesas as a basic design were syntheized. They have a pyridine skeleton and two oxazoline groups. Their structures were determined by singl crystal X-ray analysis. In the complexes, the lingad part is combining to the metal center strongly. The complexes having halogens, CO,or ethylene were also synthesized. The activity of oxidation withtheir complexes were examined to show non-selective oxidation of olefins. Aspreported in porphyrine system, the pyridine-oxazoline, non-porphyrine sytemact as carbene acceptor with diazoacetates and cyclopropene derivative. We discoved a stereospecific carbene transferreaction to stirene to give high trans selectivity, more than 95%. We can define a mechanism of carbene transfer from the complexes to olefins. The characteristic signals for the carbene unit=CH-were observed by NMR spectroscopy. In general, porphyrine systems were not easy to synthesis. However, our desinged pyridine-oxazoline ligans with ruthenium metal act very silimarly for oxidation and cyclopropanation. In next steps, we are expecting to demonstrate high catalytic activity of their complexes.

以非卟啉过渡金属配合物为基础设计合成了非卟啉过渡金属配合物。它们有一个吡啶骨架和两个恶唑啉基团。通过单晶X射线衍射分析确定了它们的结构。在配合物中，lingad部分与金属中心强烈结合。还合成了具有卤素、CO或乙烯的配合物。考察了它们的配合物对烯烃的氧化活性，结果表明它们对烯烃具有非选择性氧化作用。在卟啉体系中，吡啶-恶唑啉非卟啉体系作为卡宾受体与重氮乙酸酯和环丙烯衍生物反应。我们发现了一个立体专一的卡宾转移反应，得到了95%以上的高反式选择性。我们可以定义一个机制，从配合物的卡宾转移到烯烃。通过NMR光谱观察到卡宾单元= CH-的特征信号。卟啉体系一般不易合成。然而，我们设计的吡啶-恶唑啉配体与钌金属的氧化和环丙烷化作用非常相似。在下一步的工作中，我们期望证明它们的配合物具有高的催化活性。

项目成果

H.Nishiyama: "New Chiral. Ruthenium Bis(cxazolinyl)pyridine Catalyst. Efficient Asymmetric Cyclopropanation of Olefins and Diazoaietates" JAm. Chem. Soc. 116. 2223-2224 (1994)

H.Nishiyama：“新手性。钌双(cxazolinyl)吡啶催化剂。烯烃和重氮乙酸酯的高效不对称环丙烷化”JAm。

Hisao Nishiyama: "Ruthenium (II) Cl_2-Bis (oxazolinyl) bipyridine Conplex." Chem.Lett.1111-1114 (1994)

Hisao Nishiyama：“钌 (II) Cl_2-双（恶唑啉基）联吡啶络合物。”

H.Nishiyama: "Formation of a Vinylcarbene Complex. of Chinal.[Bis(4-isopropyloxa-zolin-2-yl)pyridine dlchlcro ruthenium(II) from 3.3-Diphenylcyclopropene" Chem. Lett.599-600 (1995)

H.Nishiyama：“从 3.3-二苯基环丙烯中形成乙烯基碳烯配合物。Chinal.[双(4-异丙基恶唑啉-2-基)吡啶二氯钌(II)”。

H.Nishiyama: "Chiral Ruthenium(II)-Bis(2-oxazolinyl)pyridine Complexes, Asymmetric Catalysis Cyclopropanation of Olefins and Diazoacetates" Bull. Chem. Soc. Jpn. 68. 1247-1262 (1995)

H.Nishiyama：“手性钌(II)-双(2-恶唑啉基)吡啶配合物，烯烃和重氮乙酸酯的不对称催化环丙烷化”公报。

Soon-Bong Park: "Trimethylsilylcarbene and Bis (trimethylsilgl) Form aldehy de Azine Copmplex of Chiral Bis (4-isipropyloxazalinyl) pridine dichlororuthenium (II)" J.Chem.Soc.Chem.Commun.1315-1316 (1994)

Soon-Bong Park：“三甲基硅基卡宾和双 (三甲基硅基) 形成手性双 (4-异丙基恶唑啉基) 吡啶二氯钌 (II) 的醛 de 吖嗪复合物” J.Chem.Soc.Chem.Commun.1315-1316 (1994)