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Development of Practical Electrolytic Partial Fluorination Processes of Heterocyclic Compounds Towards Biological Activities

Research Project

Project/Area Number 07555278
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section試験
Research Field 有機工業化学
Research InstitutionTokyo Institute of Technology

Principal Investigator

FUCHIGAMI Toshio  Tokyo Institute of Technology, Interdisciplinary Graduate School of Science and Engineering, Associate Professor, 大学院・総合理工学研究科, 助教授 (10016701)

Co-Investigator(Kenkyū-buntansha) 昆野 昭則  東京工業大学, 大学院・総合理工学研究科, 助手 (50205572)
Project Period (FY) 1995 – 1996
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥5,200,000 (Direct Cost: ¥5,200,000)
Fiscal Year 1996: ¥2,400,000 (Direct Cost: ¥2,400,000)
Fiscal Year 1995: ¥2,800,000 (Direct Cost: ¥2,800,000)
KeywordsBiologically active compounds / Fluorinated heterocycles / Electrolytic partial fluorination / Anodic oxidation / Fluoride salts / Electrode process / Fluorodesulfurization
Research Abstract

Since introduction of fluorine atom (s) into organic molecules sometimes enhances markedly their biological activities, the development of efficient direct fluorination methods has been becoming increasingly important. However, selective direct fluorination has been underdeveloped so far owing to lack of selectivity, the low nucleophilicity of fluoride ions, and passivation of the anode. Although many heterocyclic compounds possess biological activities, there have been few examples of their successful selective fluorinations. On the other hand, we have shown that an anodic method is a quite powerful for the selective direct fluorination of various heteroatom compounds such as sulfides.
From these view points, we have developed highly efficient and safe methods for selective anodic partial fluorination of various heterocycles towards bioligical activities as follows. 1) Development of Fluorinated Supporting Electrolytes and Clarification of Their Electrochemical Properties : Since fluor … More ide salts as a supporting electrolyte greatly affect anodic fluorination, we developed entirely new types of fluorinated supporing electrolytes and clarified their electrochemical properties such as potential windows. 2) Selective Anodic Monofluorination of Sulfur-containing Heterocycles : Electroplyutic conditions for anodic monofluorination of various sulfur-containing heterocycles such as thiolanones, oxathiolanones, dithiolanones, and 3H-1,4-benzooxathian-2-ones were optimized using various supporting fluoride salts in order to establish the highly efficient anodic fluorination method. 3) Direct Anodic Monofluorination of Nitrogen-containing Heterocycles : Electrolytic conditions for anodic monofluorination of various nitorgen-containing heterocycles such as oxindoles and tetrahydroisoquinolines were optimized using various anode materials and fluoride supporting electrolytes. 4) Indirect anodic monofluorodesulfurization of beta-phenylsulfenyl beta-lactams was successfully performed by using a catalytic amount of triarylamine mediators. 5) Screening test of biological activities of anodically fluorinated heterocycles was done and fluorothiolanones were found to show strong PLA2 inhibitory activity.
Thus, we have demonstrated that our develped electrolytic fluorination can be widely applicable and should be a versatile process for manufacturing various types of biologically active heterocyclic compounds. Less

Report

(3 results)
  • 1996 Annual Research Report   Final Research Report Summary
  • 1995 Annual Research Report
  • Research Products

    (13 results)

All Other

All Publications (13 results)

  • [Publications] 成塚智: "Electrosyrthesis of 4,4-Dimethyl-2-ethoxycarbonyl-5-flucro-3-thiolanones : Highly Potent Human Type II PLAZ Innibitors" Bioorganic & Medicinal Chemistry Lelfers. 5. 1293-1294 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Ayman W.Eriar: "A Novel Synthesis of Fluorothieno [2,3-b] pyridines Using Anodic Fluorination of Heteroyclic Sulfides as a Key Step" The Journal of Organic Chemistry. 60. 7654-7659 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 淵上寿雄: "有機化合物の選択的電解フッ素化" 有機合成化学協会誌. 55(印刷中). (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 淵上寿雄: "ハロゲンを鍵元素とする有機電解合成" 電気化学会誌. 65(印刷中). (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Narizuka: "Electrosynthesis of 4,4-Dimethyl-2-ethoxycarbonyl-5-fluoro-3-thiolanones : Highly Potent Human Type II PLA2 Inhibitors" Bioorganic & Medicinal Chemistry Letters. 5. 1293-1294 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] A.W.Erian: "A Novel Synthesis of Fluorothieno [2,3-b] pyridines Using Anodic Fluorination of Heterocyclic Sulfides as a Key Step" The Journal of Organic Chemistry. 60. 7654-7659 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Fuchigami: "Selective Electrolytic Fluorination of Organic Compounds" Journal of Synthetic Organic Chemistry Japan. 55, No.4 (in press). (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] T.Fuchigami: "Electroorganic Synthesis Using Halogen as a Key Element" DENKI KAGAKU. 65, No.8 (in press). (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] 淵上寿雄: "Selective Indirect Anodic Fluormation of Dithioacetals using a Bromine Mediator" The Journal of Electroaral.Chemistry. 414. 81-84 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 藤田寿康: "Electrosynthesis of Novel Hypervalert Iodobenzene chlorofluorldes and Its Application to Indirect Anodic gen-Difluorination" Tetrahedrcor teffers. 37・27. 4725-4728 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] 淵上寿雄: "有機化合物の選択的電解フッ素化" 有機合成化学協会誌. 55・4(印刷中). (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] 淵上寿雄: "A Novel Synthesis of Fluorothieno〔L2,3-6〕pyridines Using Anodic Fluorination of Heterocyclic Sulfides as a Key Step" The Journal of Organic Chemistry. 60. 7654-7659 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] 淵上寿雄: "Electrosynthesis of 4,4-Dimethyl-2-eohoxycarboyl-5-fluoro-3-thiolareres:Highly Potent Human Type II PLAZ Inhibitors" Bioorganic & Medicinal Chemistry Letters. 5. 1293-1294 (1995)

    • Related Report
      1995 Annual Research Report

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Published: 1995-04-01   Modified: 2016-04-21  

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