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SYNTHESIS OF ASYMMETRIC PORPHYRIN AND ENANTIOSELECTIVE OXYGENATION USING CHIRAL PORPHYRIN IRON COMPLEX

Research Project

Project/Area Number 62470082
Research Category

Grant-in-Aid for General Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field 有機工業化学
Research InstitutionDOSHISHA UNIVERSITY

Principal Investigator

HASHIMOTO Shizunobu  DOSHISHA UNIVERSITY, PROFESSOR, 工学部, 教授 (90066027)

Co-Investigator(Kenkyū-buntansha) TAMARU Yoshinao  KYOTO UNIVERSITY, ASSOCIATE PROFESSOR, 工学部, 助教授 (80026319)
KANO Koji  DOSHISHA UNIVERSITY, PROFESSOR, 工学部, 教授 (60038031)
Project Period (FY) 1987 – 1988
Project Status Completed (Fiscal Year 1988)
Budget Amount *help
¥7,800,000 (Direct Cost: ¥7,800,000)
Fiscal Year 1988: ¥3,200,000 (Direct Cost: ¥3,200,000)
Fiscal Year 1987: ¥4,600,000 (Direct Cost: ¥4,600,000)
Keywordsmodel of cytochrome P-450 / alkene / oxygenation / reaction mechanism / optically active amine / asymmetric oxygenation / bovin serum albumin / 水溶性ポルフィリン / チトクロームPー450モデル / 酸素化反応 / 水溶性ポルフィリン錯体 / 鉄テトラフェニルポルフィン / チトクロームPー450 / スチレン / 環状アルケン / 1ーフェニルエタノール / ベンジルアルコール
Research Abstract

The oxygenation of various alkenes using Fe(III)tetraphenylporpine (FeTPP) as a catalyst has been studied in benzene-ethanol containing NaBH_4 and diphenyl-disulfide. The final products are the alcohols and the reactoins can be regarded as the addition of H_2O to the alkenes which follows a Markovnikov's rule. The detailed study on the oxygenation of styrene suggests the reaction mechanism involving reduction of Fe(III)TPP to Fe(II)TPP by BH^-_, coordination of O_2 to Fe(II)TPP, formation of dioxetane of styrene, hydride reduction of the dioxetane to yield acetophenone and benzaldehyed, and reduction of these carbonyl compounds by BH^-_. The proposed mechanism indicates that the enantioselective oxygenation of alkenes catalyzed by an asymmetric Fe-porphyrin cannot be realized in this system. Then we have examined the oxygenation of optically active schiff bases of 2-methylcyclohexanone. The reactions of the schiff bases in toluene containing Fe(III)TPP, 4-methoxyphenol, and CaH_2 and the hydrolyses provide 2-hydroxy-2-methylcyclonexanone in low optical yields (0-26 %e.e.). In order to improve the cytochrome P-450 model system, the formation of the complexes of water-soluble porphyrins and bovine serum albumin (BSA) has been tested. BSA forms the stable complexes with cationic porphyrins. Such system may be used as an artificial cytochrome P-450.

Report

(3 results)
  • 1988 Annual Research Report   Final Research Report Summary
  • 1987 Annual Research Report
  • Research Products

    (9 results)

All Other

All Publications (9 results)

  • [Publications] KANO,Koji: Bull.Chem.Soc.Jpn.60. 1281-1287 (1987)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] KANO,Koji: J.Phys.Chem.91. 6614-6619 (1987)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] KANO,Koji: J.Phys.Chem.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Koji,KANO: "SELF AGGREGATION OF CATIONIC PORPHYRIN IN WATER" Bull. Chem. Soc. Jpn.60. 1281-1287 (1987)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Koji,KANO: "FLUORESCENCE QUENCHING OF A CATIONIC PORPHYRIN BY CATIONIC AND ANIONIC AROMATICS. Formation of ground-STATE COMPLEXES" J. Phys. Chem.91. 6614-6619 (1987)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Koji,KANO: "CATIONIC PORPHYRINS IN WATER. ^1H NMR AND FLUORESCENCE STUDIES ON DIMER AND MOLECULAR COMPLEX FORMATION" J. Phys. Chem.submitted.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Koji,KANO: Bull.Chem.Soc.Jpn.60. 1281-1287 (1987)

    • Related Report
      1988 Annual Research Report
  • [Publications] Koji,KANO: J.Phys.Chem.91. 6614-6619 (1987)

    • Related Report
      1988 Annual Research Report
  • [Publications] Koji,KANO: J.Phys.Chem.

    • Related Report
      1988 Annual Research Report

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Published: 1987-04-01   Modified: 2016-04-21  

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