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.

非卟啉过渡金属复合物作为基本设计是合成的。他们有一个吡啶骨骼和两个恶唑啉基。它们的结构是通过SINGL Crystal X射线​​分析确定的。在综合体中，lingad部分正与金属中心结合在一起。还合成了具有卤素，CO或乙烯的复合物。检查了用特种络合物的氧化活性，以显示烯烃的非选择性氧化。在卟啉系统，吡啶 - 恶唑啉，非孢子级肌酸作为卡宾受体和环丙烯衍生物中，迅速发展。我们溶解了立体的卡宾转移反应以搅拌以产生高的反式选择性，超过95％。我们可以定义从配合物到烯烃转移的机制。 NMR光谱学观察到Carbene单元的特征信号。通常，卟啉系统不容易合成。然而，我们的丁吡啶 - 恶唑啉长甘甘甘氨酸具有金属的作用非常小，用于氧化和环芽顺化。在下一步中，我们期望证明其复合物的高催化活性。

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)