STUDIES ON THE STRUCTURE AND CATALYSIS OF NONHEMEIRON COMPLEXES WHICH FUNCTION ENZYME-LIKE CATALYTIC ACTIVITY

具有类酶催化活性的非半铁基复合物的结构和催化作用的研究

• 批准号: 02453078
• 负责人: FUNABIKI Takuzo
• 金额: $ 3.58万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-02453078/
• 关键词: ENZYME-LIKE FUNCTION; NONHEMEIRON COMPLEXES; CATECHOLDIOXYGENASE; MONOOXYGENASE; HYDROXYLATION; OXYGENATION; CARBONYLATION; IRON-OXENOID ACTIVE SPECIES; 酵素類似機能; カテコ-ルジオキンゲナ-ゼ; モノオキシゲナ-ゼ; 酵素酸化反応; 酵素類似触媒反応; 非ヘム鉄錯体; カテゴルの反酸素化開製; カテコ-ル鉄錯体; モノオ

Structure and function of the model complex of nonheme iron dioxygenases and mono-oxygenases were studied on the bases of product analysis of organic products and spectroscopy of the intermediate iron complexes in the solution. Catecholdioxygenase model reaction was correlated by using catecholatoiron for monooxygenase model reaction.1.Catecholdioxygenase Model SystemOn the basis of the catalytic reactivity, we have proposed that the catechol forms catechotoiron(III) complexes which may be in equilibrium with semiquinonatoiron(II) complexes as direct intermediates for the reaction with oxygen. Spectroscopy has indicated the formation of the catecholatoiron(III), but no direct evidence for the semiquinonatoiron(II) has been obtained. In this study we have isolated catecholatoiron(III) complexes. Structure of the complexes in solution was studied spectroscopically, e.g. ESR, Mossbauer, EXAFS, specially by ^1H and ^2H NMR, and the strong radical character of the catecholate ligand , supporting the semiquinonateiron species as an direct active species, has been clearly shown.2. Monooxygenase Model SystemWe have developed the catecholoteiron(III) complex/hydroquinones/O2 for the catalytic monooxygenation of aromatics, cyclic and acyclic saturated hydrocarbons in nonaqueous organic solvent such as acetonitile. One of the important and interesting results is the great dependence of selectivity on the pyridine concentration. In the low pyridine concentration, hydroxylation is the main reaction, but in pyridine carbonylation is the main reaction. The reactivity also depends on the substituents on the hydroquinones. Active species was found to be iron-oxygen species rather than the hydroxyl radical.

通过有机产物的产物分析和溶液中铁络合物的光谱分析，研究了非血红素铁双加氧酶和单加氧酶模型络合物的结构和功能。以邻苯二酚铁为单加氧酶模型反应，关联了邻苯二酚双加氧酶模型反应。1.邻苯二酚双加氧酶模型体系基于邻苯二酚的催化活性，我们提出邻苯二酚形成邻苯二酚铁（III）配合物，该配合物可能与半醌铁（II）配合物处于平衡状态，作为与氧反应的直接中间体。光谱表明形成的儿茶酚铁（III），但没有直接证据的semiquinonatoiron（II）已获得。在这项研究中，我们已经分离出儿茶酚铁（III）配合物。通过ESR、Mossbauer、EXAFS等光谱技术，特别是^1H和^2H NMR，研究了配合物在溶液中的结构，明确了邻苯二酚配体的强自由基特征，支持半醌铁物种作为直接活性物种.单加氧酶模型体系我们开发了邻苯二酚铁（III）配合物/对苯二酚/O2催化剂，用于在非水有机溶剂如乙腈中催化芳烃、环状和无环饱和烃的单加氧反应。其中一个重要而有趣的结果是选择性对吡啶浓度有很大的依赖性。在低吡啶浓度下，羟基化反应为主，而在吡啶浓度下，羰基化反应为主。反应性还取决于对苯二酚上的取代基。活性物种被发现是铁氧物种，而不是羟基自由基。

项目成果

Takuzo Funabiki: "Strong Radical Character of the Catecholate Ligand of Catecholato(pyridine)Iron Complexes Involved in the Catecholdioxygenase-model Reaction" Chem.Lett.2143-2145 (1991)

Takuzo Funabiki：“参与儿茶酚二加氧酶模型反应的儿茶酚（吡啶）铁配合物的儿茶酚酸配体的强自由基特性”Chem.Lett.2143-2145（1991）

Takuzo Funabiki,Takehiro Toyoda, Hiroyuki Ishida, Motoyoshi Tsujimoto, Satoshi Ozawa, and Satohiro Yoshida: "Oxygenase Model Reactions.Part * . Hydroxylation of Aromatic Compounds by Catecholatoiron Complex/Hydroquinones/O_2 in Acetonitrile" J.Mol.Catal.6

Takuzo Funabiki、Takehiro Toyoda、Hiroyuki Ishida、Motoyoshi Tsujimoto、Satoshi Ozawa 和 Satohiro Yoshida：“氧合酶模型反应。第 * 部分。乙腈中儿茶酚铁络合物/氢醌/O_2 对芳香族化合物的羟基化”J.Mol.Catal.6

T.Funabiki,T.Inoue,H.Kojima,T.Konishi,S.Yoshida: "ExtendedーHuckel Study on the Odygen Insertion into the Aromatic Ring by the Model Complexes for Catecholーdioxygenases" J.Molelcular Catalysis. 59. 367-371 (1990)

T.Funabiki、T.Inoue、H.Kojima、T.Konishi、S.Yoshida：“通过儿茶酚双加氧酶模型复合物将氧插入芳香环的扩展休克尔研究”J.分子催化。 -371 (1990)

Takuzo Funabiki: "Oxidation of hydroxylbenzenes with oxygen catalyzed by supported metal chloride catalysts in aprotic solvents. Part 1.Effects of supports and solvents on reactivity" J.Mol.Catal.,. 69. 407-418 (1992)

Takuzo Funabiki：“在非质子溶剂中由负载型金属氯化物催化剂催化的氧对羟基苯的氧化。第 1 部分：载体和溶剂对反应性的影响”J.Mol.Catal.,。

Takuzo Funabiki: "Characteristic Effect of pyridine on the NIH Shift and Selectivity in the Monooxygenation of Aromatic Compounds Catalyzed by a Nonheme Iron Complex/Hydroquinones/O_2 System" Chem.Lett.1279-1282 (1992)

Takuzo Funabiki：“吡啶对非血红素铁络合物/氢醌/O_2 系统催化的芳香族化合物单氧化反应中 NIH 位移和选择性的特征影响”Chem.Lett.1279-1282 (1992)