• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to project page

1996 Fiscal Year Final Research Report Summary

Studies on the Synthesis of Dynemicin Analogues and their Reaction Mechanisms

Research Project

Project/Area Number 07457521
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemical pharmacy
Research InstitutionThe University of Tokushima

Principal Investigator

SHIBUYA Masayuki  Faculty of Pharmaceutical Sciences, The University of Tokushima, Professor, 薬学部, 教授 (40027066)

Co-Investigator(Kenkyū-buntansha) SHISHIDO Kozo  Institute for Medicinal Resources, Faculty of Pharmaceutical Sciences, The Unive, 薬学部・附属医薬資源教育研究センター, 教授 (20006349)
Project Period (FY) 1995 – 1996
Keywordsenyne-allene / synthesis / enzyme-inhibition / cascade / Dynemicin / radical / Vitamin B6
Research Abstract

Dynemicins possessing the characteristic cis-hex-3-ene-1,5-diynyl group have attracted considerable attention due to the generation of a phenylene biradical which is responsible for DNA strand scission. Designing the structurally simplified enediyne congeners retaining the impressive DNA cleaving properties is of great importance for potential use in chemotherapy or as tools for biotechnology. Ongoing research concerned with the development of bioactive enediyne mimics has required large quantities of acyclic enediynes. We initiated the research for the convenient and practical synthesis of of the open chain enediyne derivatives by simple elimination of tert-hydroxy group. By using above method, we synthesized several model enediynes which produce biradical species via enyne-allene intermediates. One of them is the model compounds which produce biradicals under acidic conditions, and the other is the enediynes which produce biradicals by ester-hydrolysis. Both model compounds produced carbon biradicals by their characteristic cascade reactions initiated by triggering devices. On the way of these investigations, we found that the biradicals transformed into zwitterionic species, and this reaction mechanisms were investigated. On the other hand, the acyclic enediyne possessing an aminomethyl group was designed and synthesized as a potential substrate for pyridoxal-dependent enzymes. This compound was shown to give cycloaromatized products by the reaction with pyridoxal or isonicotinaldehyde via the toluene biradical intermediate.

  • Research Products

    (12 results)

All Other

All Publications (12 results)

  • [Publications] 渋谷 雅之: "A convenient synthesis of acyclic conjugated enediynes" Tetrahedron Letters. 36. 897-898 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 渋谷 雅之: "pH Dependent Cycloaromatization of Enediyne Model Compounds" Tetrahedron Letters. 36. 9165-9168 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 渋谷 雅之: "A New Method for the Preparation of Phenyl-Substituted cis-Enediyne from a Phthalide Derivative" Chem.Pharm.Bull.44. 2186-2188 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 渋谷 雅之: "Cycloaromatization of Enediyne Model Compounds via a Reaction Cascade Triggered by Hydrolysis of the α-Alkynylmalonates" Tetrahedron Letters. 37. 865-868 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 渋谷 雅之: "Pyridoxal-Mediated Cycloaromatization of an Enediyne Model System" Tetrahedron Letters. 37. 5397-5400 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 宍戸 宏造: "Diastereoselective Oxidation of Mercapturates to Mercapturate Sulfoxides" Bioorg.& Med.Chem.Lett.937-940 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Shibuya, Y.Sakai, and Y.Naoe: "A Convenient Synthesis of Acyclic Conjugated Enediynes" Tetrahedron Letters. 36. 897-898 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Naoe, J.Kikuishi, K.Ishigaki, H.Iitsuka, H.Nemoto, and M.Shibuya: "pH Dependent Cycloaromatization of Enediyne Model Compounds" Tetrahedron Letters. 36. 9165-9169 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Shibuya, M.Wakayama, Y.Naoe, T.Kawakami, K.Ishigaki, H.Nemoto, H.Shimizu, Y.Nagao: "Cycloaromatization of Enediyne Model Compounds via a Reaction Cascade Triggered by Hydrolysis of the alpha-Alkynylmalonates" Tetrahedron Letters. 37. 865-868 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Wakayama, H.Nemoto, and M.Shibuya: "Pyridoxal-Mediated Cycloaromatization of an Enediyne Model System" Tetrahedron Letters. 37. 5397-5400 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.Nemoto, J.Kikuishi, and M.Shibuya: "A New Method for the Preparation of Phenyl-Substituted cis-Enediyne from a Phthalide Derivative" Chem.Pharm.Bull. 44. 2186-2188 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Nakamura, K.Goto, M.Kondo, S.Naito, M.Bando, M.Kido, K.Shishido: "Diastereoselective Oxidation of Mercapturates to Mercapturate Sulfoxides" Bioorg.& Med.Chem.Lett.937-940 (1996)

    • Description
      「研究成果報告書概要(欧文)」より

URL: 

Published: 1999-03-09  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi