Development ot highly selective oxygenation by oxygenase-model metal-oxygen active species and clarification of the mechanisms of selectivity control

加氧酶模型金属氧活性物质高选择性氧化的发展及选择性控制机制的阐明

• 批准号: 09450297
• 负责人: FUNABIKI Takuzo
• 金额: $ 10.11万
• 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: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09450297/
• 关键词: Nonheme Iron Complex; Oxygnases; Monooxygenases; Dioxygenases; Catechols; Oxygenative Cleavages of Aromatics; Chlorocatechols; Development of Oxygenase Function; 酵素機能発現

Highly selective oxygenations by nonheme metal-oxygen species were developed and mechanisms of the control of selectivity were studied spectroscopically.Selective intradiol oxygenation of catechols by iron(III) complexes has been extensively studied. We have developed the selective oxygenation of chlorocatechols. Products include dehydrochlorinated products, that opens the new process for the dechlorination of chloroaromatics which are environmental pollutant. The model intermediate complexes, chlorocatecholatoiron complexes have been isolated. Their configurational and electronic structures were analyzed by XAFS, magnetic susceptibility, EPR, electronic absorption spectra. It was indicated that the complexes should be represented by lron(II)-semiquinonate rather than lron(III)-catecholate complexes. Another dioxygenase model reactions studied are lipoxygenase model which oxygenates linoleic acid, tyrosine hydroxylase model which hydroxylates t-butylphenol to give o-catechol, and a-keto acid dependent oxygenase which oxygenates alkenes to give epoxides and alkanes to give alcohols. Mechanistic investigations were performed in addition to the synthetic works. These reactions are under further studies to develop good catalytic oxygenation systems and to get mechanistic information for enzymatic oxygenations.

高选择性氧化的非血红素金属氧物种和控制的选择性的机理进行了研究spectroscopically. Selectiveintradioloxidation的儿茶酚的铁（III）配合物已被广泛研究。我们已经开发了氯邻苯二酚的选择性氧化。产品包括脱氯化氢产品，为环境污染物氯代芳烃的脱氯开辟了新工艺。模型中间体配合物，氯儿茶酚铁配合物已被分离。用XAFS、磁化率、EPR、电子吸收光谱等方法分析了它们的构型和电子结构。结果表明，配合物应是铁（II）-半醌型配合物，而不是铁（III）-儿茶酚型配合物。研究的另一种双加氧酶模型反应是氧化亚油酸的脂氧合酶模型，羟基化叔丁基苯酚以得到邻苯二酚的酪氨酸羟化酶模型，以及氧化烯烃以得到环氧化物和氧化烷烃以得到醇的α-酮酸依赖性加氧酶。除了合成工作外，还进行了机理研究。这些反应正在进一步研究中，以开发良好的催化氧化体系，并获得酶促氧化的机理信息。

项目成果

Takuzo Funabiki: "Dioxygenases" Oxygenases and Model Systems.19-104 (1997)

Takuzo Funabiki：“双加氧酶”加氧酶和模型系统.19-104 (1997)

Sakae Takenaka: "Reaction Mechanism of Photooxidation of Propane over Alkali-Ion-Modified Silica-Supported Vanadium Pentaoxide under Irradiation by Visible Light" J.Chem.Soc.,Faraday Trans.93. 4151-4158 (1997)

Sakae Takenaka：“可见光照射下碱离子改性二氧化硅负载五氧化二钒上丙烷光氧化的反应机制”J.Chem.Soc.，Faraday Trans.93。

Takuzo Funabiki: "X-ray crystallographic and absorption spectroscopic analyses of structures of catecholato(pyridine)iron chloride complexes in relevance to functional model complexes for catechol 1,2-dioxygenases" Inorg.Chim.Acta. 275-276. 222-229 (1998)

Takuzo Funabiki：“儿茶酚（吡啶）氯化铁复合物结构的 X 射线晶体学和吸收光谱分析与儿茶酚 1,2-双加氧酶功能模型复合物的相关性”Inorg.Chim.Acta。

Takuzo Funabiki: "ortho-Hydroxylation of 4-Tert-Butylphenol by Nonheme Iron (III) Complexes as a Functional Model Reaction for Tyrosine Hydroxylase" J.Chem.Soc.,Chem.Commun.151-152 (1997)

Takuzo Funabiki：“非血红素铁 (III) 复合物对 4-叔丁基苯酚的邻羟基化作为酪氨酸羟化酶的功能模型反应”J.Chem.Soc.,Chem.Commun.151-152 (1997)

H.Yoshida: "Epoxidation of Propene by Gaseous Oxygen over Silica and Mg-loaded Silica under Photoirradiation" J.Catal.171. 351-357 (1997)

H.Yoshida：“光照射下二氧化硅和负载镁的二氧化硅上气态氧对丙烯的环氧化”J.Catal.171。