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

Research Project

Project/Area Number 09450297
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field 触媒・化学プロセス
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

FUNABIKI Takuzo  Kyoto University, Graduate School of Engineering, Associate Professor, 工学研究科, 助教授 (70026061)

Co-Investigator(Kenkyū-buntansha) TANAKA Tsunehiro  Kyoto Univerisity, Graduate School of Engineering, Associate Professor, 工学研究科, 助教授 (70201621)
TAKANO Mikio  Kyoto University, Insitute for Chemical Research, Professor, 化学研究所, 教授 (70068138)
SUGIURA Yukio  Kyoto University, Insitute for Chemical Research, Professor, 化学研究所, 教授 (40025698)
Project Period (FY) 1997 – 1998
Project Status Completed (Fiscal Year 1998)
Budget Amount *help
¥15,800,000 (Direct Cost: ¥15,800,000)
Fiscal Year 1998: ¥5,900,000 (Direct Cost: ¥5,900,000)
Fiscal Year 1997: ¥9,900,000 (Direct Cost: ¥9,900,000)
KeywordsNonheme Iron Complex / Oxygnases / Monooxygenases / Dioxygenases / Catechols / Oxygenative Cleavages of Aromatics / Chlorocatechols / Development of Oxygenase Function / 酵素機能発現
Research Abstract

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.

Report

(3 results)
  • 1998 Annual Research Report   Final Research Report Summary
  • 1997 Annual Research Report
  • Research Products

    (27 results)

All Other

All Publications (27 results)

  • [Publications] 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)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Takuzo Funabiki: "Oxygenative cleavage of chlorocatechols with molecular oxygen catalyzed by nonheme iron(III)complexes and its relevance to chlorocatechol dioxygenases" Angew Chem.Inern.Ed.Eng.37. 513-515 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] 船引卓三: "鉄錯体による酵素類似型酸素化反応" 触媒. 40. 310-317 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] 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.102. 151-152 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Takuzo Funabiki: "Dioxygenases" Oxygenases and Model Systems.19-104 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Takuzo Funabiki: "Iron Model Studies on Dioxyenases" Oxygenases and Model Systems.105-156 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Takuzo Funabiki: "Oxygenases and Model Systems." Kluwer Academic Publishers, Dordrecht/Boston/London,393 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] 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)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Takuzo Funabiki: "Oxygenative cleavage of chlorocatechols with molecular oxygen catalyzed by nonheme iron(III)complexes and its relevance to chlorocatechol dioxygenases" Angew Chem.Inern.Ed.Eng.37. 513-515 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Takuzo Funabiki: "Enzyme-lime oxygenations catalyzed by iron complexes" Catalyst. 40. 310-317 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] 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)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Takuzo Funabiki: "Dioxygenases" Oxygenases and Model Systems.19-104. (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Takuzo Funabiki: "Iron Model Studies on Dioxyenases" Oxygenases and Model Systems.106-156. (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Takuzo Funabiki: "Oxygenases and Model Systems." Catalysis by Mtetal Complexes, No19, Kluwer Academic Publishers, Dordrecht/Boston/London. 1-393 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] 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)

    • Related Report
      1998 Annual Research Report
  • [Publications] Takuzo Funabiki: "Oxygenative cleavage of chlorocatechols with molecular oxygen catalyzed by nonheme iron(III) complexes and its relevance to chlorocatechol dioxygenases" Angew Chem.Inern.Ed.Eng.37. 513-515 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 船引卓三: "鉄錯体による酵素類似型酸素化反応" 触媒. 40. 310-317 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Sakae Takenaka: "Structures of Molybdenum Species in Silica-Supported Molybdenum Oxide and Alkali-Ion-Modified Silica-Supported Molybdenum Oxide" J.Phys.Chem.B. 102. 2906-2909 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Yoshiumi Kohno: "Identification and Reactivity of a Surface Intermediate in the Photoreduction of CO2 with H2 over ZrO2" J.Chem.Soc.,Faraday Trans.94. 1875-1880 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Sakae Takenaka: "Effect of Alkali Ion Addition to Silica-supported Molybdenum Oxide on Photocatalysis: Photooxidation of Propane and Propene, and Photo-Assisted Metathesis Reaction of Propene" J.Chem.Soc.,Faraday Trans.94. 695-670 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] 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. (In press). (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] Takuzo Funabiki: "Oxygenative cleavage of chlorocatechols with molecular oxygen catalyzed by nonheme iron (III) complexes and its relevance to chlorocatechol dioxygenases" Angew Chem.Inern.Ed.Eng.,. 37. 513-515 (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] 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)

    • Related Report
      1997 Annual Research Report
  • [Publications] Sakae Takenaka: "Structure of Active Species in Alkali-Ion-Modified Silica-Supported Vanadium Oxide" J.Phys.Chem.B. 101. 9035-9045 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] H.Yoshida: "Epoxidation of Propene by Gaseous Oxygen over Silica and Mg-loaded Silica under Photoirradiation" J.Catal.171. 351-357 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 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)

    • Related Report
      1997 Annual Research Report
  • [Publications] Takuzo Funabiki: "Oxygenases and Model Systems." Kluwer Academic Publishers,Dordrecht/Boston/London,393 (1997)

    • Related Report
      1997 Annual Research Report

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Published: 1997-04-01   Modified: 2016-04-21  

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