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.

在溶液中，在有机产物的产物分析和中间铁络合物的乘积分析的基础上研究了非血红素铁二加氧酶和单氧酶的模型复合物的结构和功能。通过使用Catecholatoiron对单加氧酶模型反应进行Catecholdioxygyase模型的反应。1.Catecholdioxygyase模型Systemon Systemon是催化反应性的基础，我们提出，Catechol形成儿茶素铁（III），与SemiquinonatoRione（II II）相应的均具有直接反应（II）的配合物，该复合物与直接反应（II）形成式互联物。光谱法表明Catecholatoiron（III）的形成，但尚未获得Semiquinonatoiron（II）的直接证据。在这项研究中，我们有分离的Catecholatoiron（III）复合物。溶液中络合物的结构进行了光谱研究，例如ESR，Mossbauer，Exafs，特别是由 ^1H和 ^2H NMR，以及catechalice配体的强大激进特征，支持半苯二甲酸酯物种作为直接活性物种，已清楚地表明。2。单加氧化酶模型Systemwe已经开发了用于芳香族剂，环状和无环饱和的烃类催化单氧化的catecholoteionl（III）复合物/氢喹酮/O2。重要且有趣的结果之一是选择性对吡啶浓度的极大依赖性。在低吡啶浓度中，羟基化是主要反应，但在吡啶羰基化中是主要反应。反应性还取决于氢喹酮上的取代基。发现活性物种是铁氧物种，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）

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,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

Takuzo Funabiki et al.: "Oxygenase Model Reactions.Part II.Hydroxylation of Aromatic Compounds by Catecholatoiron Complex/Hydroquinones/O_2 in Acetonitrile" J.Mol.Cat. 61. 235-246 (1990)

Takuzo Funabiki 等人：“氧化酶模型反应。第二部分。乙腈中儿茶酚铁复合物/氢醌/O_2 对芳香族化合物的羟基化”J.Mol.Cat。