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1998 Fiscal Year Final Research Report Summary

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
KeywordsNonheme Iron Complex / Oxygnases / Monooxygenases / Dioxygenases / Catechols / Oxygenative Cleavages of Aromatics / Chlorocatechols / Development of Oxygenase Function
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.

  • Research Products

    (14 results)

All Other

All Publications (14 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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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
  • [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

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Published: 1999-12-08  

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