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Phenolic oxidation towards synthesis of bioactive cyclic peptides

Research Project

Project/Area Number 15510181
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Living organism molecular science
Research InstitutionKeio University

Principal Investigator

NISHIYAMA Shigeru  Keio University, Faculty of Science and Technology, Professor, 理工学部, 教授 (20137988)

Co-Investigator(Kenkyū-buntansha) 中村 和彦  産業技術研究所, 分子細胞工学研究部門, 主任研究員 (50286647)
Project Period (FY) 2003 – 2004
Project Status Completed (Fiscal Year 2004)
Budget Amount *help
¥3,800,000 (Direct Cost: ¥3,800,000)
Fiscal Year 2004: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 2003: ¥2,800,000 (Direct Cost: ¥2,800,000)
KeywordsPhenolic oxidation / Electroorganic chemistry / Thallium(III) oxidation / Aeroplysinin-1 / Eurypamide / Calafianin / Verbenachalcone / Heliannuol / アレロパシー活性 / フェノール酸化反応 / ヘリアヌオール誘導体 / スピロソキサゾール / クロマン誘導体 / アエロプリシニン / 全合成
Research Abstract

Synthetic studies on bioactive substances including natural products by phenolic oxidation employing anodic and thallium (III) oxidation reactions as key steps, was undertaken in this research project, as follows. (1)Synthesis of eurypamides. A, B, and D was successfully accomplished by the cyclization at the diaryl ether moieties. This result attached with findings of mono-cyclic peptide carrying the inhibitory activity against MRSA. (2)Bromination of germacrene D by bromonium ion electrochemically generated, provide the new bicyclic products, structures of which were spectroscopically determined. (3)The tandem reaction involving anodic oxidation of phenol derivatives, followed by the Lewis acid arrangement, provides heliannuol E, an alleropathogenic substance of sunflower, along with its congeners. This investigation revealed that the selectivity of the arrangement reaction is conducted by stereochemistry and electric character of aromatic substituents. More effective biological activity than that of natural heliannuols, was observed among synthetic intermediates and related products. (4)The electrochemical construction of the spiroisoxazoline derivatives made it possible to synthesize aerhoplysinin-1 and calafianin, spiroisoxazoline-class marine natural products. In the former investigation, the new ring-opening of the isoxazoline to the cyanohydrin was established, and the revision of the reported structure was undertaken. (5)Verbenachalcone, an activator of the nerve-growing factor of plant origin, was successfully synthesized by anodic oxidation of phenol derivatives carrying mixed halogen-substituents, which provided a methoxy diaryl ether moiety.
0

Report

(3 results)
  • 2004 Annual Research Report   Final Research Report Summary
  • 2003 Annual Research Report
  • Research Products

    (39 results)

All 2005 2004 2003 Other

All Journal Article (31 results) Book (1 results) Patent(Industrial Property Rights) (2 results) Publications (5 results)

  • [Journal Article] Synthesis and structural revision of calafianin, a member of the spiroisoxazole family olated from the marine sponge, Aplysina gerardogreeni2005

    • Author(s)
      T.Ogamino
    • Journal Title

      Tetrahedron Letters 46

      Pages: 1083-1086

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] フェニルピルビン酸オキシムを基本骨格とする海洋生物由来の生物活性物質の化学2005

    • Author(s)
      小神野孝尚
    • Journal Title

      有機合成化学協会誌 63

      Pages: 583-593

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Synthesis and structural revision of calafianin, a member of the spiroisoxazole family isolated from the marine sponge, Aplysina gerardogreeni.2005

    • Author(s)
      T.Ogamino, S.Nishiyama.
    • Journal Title

      Tetrahedron Lett. 46

      Pages: 1083-1086

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Synthesis and structural revision of calafianin, a member of the spiroisoxazole family isolated from the marine sponge, Aplysina geradogreen2005

    • Author(s)
      T.Ogamino
    • Journal Title

      Tetrahedron Letters 46・7

      Pages: 1083-1086

    • Related Report
      2004 Annual Research Report
  • [Journal Article] フェニルピルビン酸オキシムを基本骨格とする海洋生物由来の生物活性物質の化学2005

    • Author(s)
      小神野孝尚
    • Journal Title

      有機合成化学協会誌 63・6(印刷中)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] A total synthesis of verbenachalcone, a bioactive diaryl ether from Verbena littoralis2004

    • Author(s)
      T.Tanabe
    • Journal Title

      Tetrahedron Letters 45

      Pages: 3477-3480

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Total synthesis of eurypamides, marine cyclic-isodityrosines from the Palauan sponge Microciona eurypa2004

    • Author(s)
      M.Ito
    • Journal Title

      Tetrahedron 60

      Pages: 5623-5634

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Plant-growth inhibitory activity of heliannuol derivatives.2004

    • Author(s)
      F.Doi
    • Journal Title

      Phytochemistry 65

      Pages: 1405-1411

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Electrochemical bromination of germacrene D2004

    • Author(s)
      T.Ogamino
    • Journal Title

      ELECTROCHIMICA ACTA 49

      Pages: 4865-4869

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Synthesis of chroman derivatives by the ring expansion reaction of spirodienones, and an assessment of their plant growth inhibition2004

    • Author(s)
      F.Doi
    • Journal Title

      Bulletin of Chemical Society Japan 77

      Pages: 2257-2263

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Scope and Limitation of Electrochemical Phenolic Oxidation : Synthesis of Verbenachalc one.2004

    • Author(s)
      T.Tanabe
    • Journal Title

      Proceedings - Electrochemical Society, 2004-10 (Analytical Mechanistic and Synthetic Organic Electrochemistry- 6th International M. Baizer Award Symposium in Honor of Dennis H.Evans and Masao Tokuda) 2004-10

      Pages: 157-160

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] A total synthesis of verbenachalcone, a bioactive diaryl ether from Verbena littoralis.2004

    • Author(s)
      T.Tanabe, F.Doi, T.Ogamino, S.Nishiyama.
    • Journal Title

      Tetrahedron Lett. 45

      Pages: 3477-3480

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Total synthesis of eurypamides, marine cyclic-isodityrosines from the Palauan sponge Microciona eurypa.2004

    • Author(s)
      M.Ito, M.Yamanaka, N.Kutsumura, S.Nishiyama.
    • Journal Title

      Tetrahedron 60

      Pages: 5623-5634

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Plant-growth inhibitory activity of heliannuol derivatives.2004

    • Author(s)
      F.Doi, I.Ohara, T.Ogamino, T.Sugai, K.Higashinakasu, K.Yamada, H.Shigemori, K.Hasegawa, S.Nishiyama.
    • Journal Title

      Phytochem. 65

      Pages: 1405-1411

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Electrochemical bromination of germacrene D.2004

    • Author(s)
      T.Ogamino, K.Mori, S.Yamamura, S.Nishiyama.
    • Journal Title

      ELECTROCHIMICA ACTA 49/27

      Pages: 4865-4869

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Synthesis of chroman derivatives by the ring expansion reaction of spirodienones, and an assessment of their plant growth inhibition.2004

    • Author(s)
      F.Doi, T.Ohara, T.Ogamino, K.Higashinakasu, K.Hasegawa, S.Nishiyama.
    • Journal Title

      Bull.Chem.Soc.Jpn. 77

      Pages: 2257-2263

    • NAID

      10014219176

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Scope and Limitation of Electrochemical Phenolic Oxidation : Synthesis of Verbenachal cone.2004

    • Author(s)
      T.Tanabe, F.Doi, T.Ogamino, S.Nishiyama.
    • Journal Title

      Proceedings - Electrochemical Society, 2004-10(Analytical Mechanistic and Synthetic Organic Electrochemistry- 6th International M.Baizer Award Symposium in Honor of Dennis H.Evans and Masao Tokuda)

      Pages: 157-160

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Total synthesis of eurypamides, marine cyclic-isodityrosines from the Palauan sponge Microciona eurypa.2004

    • Author(s)
      M.Ito
    • Journal Title

      Tetrahedron 60・26

      Pages: 5623-5634

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Synthesis of Chroman Derivatives by the Ring Expansion Reaction of Spirodienones, and an Assessment of their Plant Growth2004

    • Author(s)
      F.Doi
    • Journal Title

      Bulletin of the Chemical Society Japan 77・12

      Pages: 2257-2263

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Plant-growth inhibitory activity of heliannuol derivatives.2004

    • Author(s)
      F.Doi
    • Journal Title

      Phytochemistry 65・10

      Pages: 1405-1411

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Enantioselective synthesis of heliannuol E ; structural consideration of natural molecule.2003

    • Author(s)
      F.Doi
    • Journal Title

      Tetrahedron Letters 44

      Pages: 4877-4880

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Electrochemical synthesis of spiroisoxazole derivatives and its application to natural products2003

    • Author(s)
      T.Ogamino
    • Journal Title

      HETEROCYCLES 61

      Pages: 73-78

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Synthesis and structural revision of eurypamides isolated from the palanan sponge Microciona eurypa2003

    • Author(s)
      M.Ito
    • Journal Title

      Tetrahedron Letters 44

      Pages: 7949-7952

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] A new ring-opening access to aeroplysinin-1, a secondary metabolite of Verongia aerophoba.2003

    • Author(s)
      T.Ogamino
    • Journal Title

      Tetrahedron 59

      Pages: 9419-9423

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Synthetic studies on bioactive natural products employing electrochemical methodology, synthesis of heliannuol E.2003

    • Author(s)
      F.Doi
    • Journal Title

      Proceedings - Electrochemical Society, 2003-12(Mechanistic and Synthetic Aspects of Organic and Biological Electrochemistry 2003-12

      Pages: 117-120

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Enantioselective synthesis of heliannuol E ; structural consideration of natural molecule.2003

    • Author(s)
      F.Doi, T.Ogarmno, T.Sugai, S.Nishiyama.
    • Journal Title

      Tetrahedron Lett. 44

      Pages: 4877-4880

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Electrochemical synthesis of spiroisoxazole derivatives and its application to natural products.2003

    • Author(s)
      T.Ogamino, Y.Ishikawa, S.Nishiyama.
    • Journal Title

      HETEROCYCLES 61

      Pages: 73-78

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Synthesis and structural revision of eurypamides isolated from the Palauan sponge Microciona eurypa.2003

    • Author(s)
      M.Ito, M.Yamanaka, N.Kutsumura, S.Nishiyama.
    • Journal Title

      Tetrahedron Lett. 44

      Pages: 7949-7952

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] A new ring-opening access to aeroplysinin-1, a secondary metabolite of Verongia aerophoba.2003

    • Author(s)
      T.Ogamino, S.Nishiyama.
    • Journal Title

      Tetrahedron 59

      Pages: 9419-9423

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Synthetic studies on bioactive natural products employing el ectrochemical methodology, synthesis of heliannuol E.2003

    • Author(s)
      F.Doi, T.Ogamino, T.Sugai, S.Nishiyama.
    • Journal Title

      Proceedings - Electrochemical Society, 2003-12(Mechanistic and Synthetic Aspects of Organic and Biological Electrochemistry)

      Pages: 117-120

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] The chemistry of phenylpyruvic acid oxime, bioactive substances from marine origin.(in Japanese).

    • Author(s)
      T.Ogamino, S.Nishiyama.
    • Journal Title

      J.Syn.Org.Chem.Jpn. (in press)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Book] 生理活性天然物の電解合成 有機電解合成の新展開II(監修 淵上寿雄)2004

    • Author(s)
      西山 繁
    • Publisher
      シーエムシー出版
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Annual Research Report 2004 Final Research Report Summary
  • [Patent(Industrial Property Rights)] 環状イソジチロシン誘導体化合物2004

    • Inventor(s)
      西山 繁, 小畠 りか, 供田 弘
    • Industrial Property Rights Holder
      西山 繁, 小畠 りか, 供田 弘
    • Industrial Property Number
      2004-336698
    • Filing Date
      2004-11-19
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Annual Research Report 2004 Final Research Report Summary
  • [Patent(Industrial Property Rights)] 植物成長阻害剤2003

    • Inventor(s)
      西山 繁, 土居 史尚, 小神野 孝尚, 小原 大雅, 須貝 威, 長谷川 宏司, 繁森 英幸
    • Industrial Property Rights Holder
      西山 繁, 土居 史尚, 小神野 孝尚, 小原 大雅, 須貝 威, 長谷川 宏司, 繁森 英幸
    • Industrial Property Number
      2003-345896
    • Filing Date
      2003-10-03
    • Acquisition Date
      2005-04-28
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Publications] F.Doi: "Intramolecular Diels-Alder reaction leading to tricyclic derivatives as intermediates of natural products synthesis."Tetrahedron Letters. 44・26. 4877-4880 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Ogamino: "Electrochemical synthesis of spiroisoxazole derivatives and its application to natural products."HETEROCYCLES. 61. 73-78 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] M.Ito: "Synthesis and structural revision of eurypamides isolated from the palauan sponge Microciona eurypa."Tetrahedron Letters. 44・43. 7949-7952 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Ogamino: "A new ring-opening access to aeroplysinin-1, a secondary metabolite of Verongia aerophoba."Tetrahedron. 59・47. 9419-9423 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Tanabe: "A total synthesis of verbenachalcone, a bioactive diaryl ether from Verbena littoralis"Tetrahedron Letters. 44(印刷中). (2004)

    • Related Report
      2003 Annual Research Report

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Published: 2003-04-01   Modified: 2016-04-21  

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