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1997 Fiscal Year Final Research Report Summary

Synthetic Studies on Nitrogen Containing Natural Products

Research Project

Project/Area Number 08457582
Research Category

Grant-in-Aid for Scientific Research (B)

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

Principal Investigator

FUKUYAMA Tohru  The University of Tokyo, Graduate School of Pharmaceutical Sciences, Professor, 大学院・薬学系研究科, 教授 (10272486)

Project Period (FY) 1996 – 1997
Keywordsindole Synthesis / Tabersonine / Vincadifformine / protective group / sulfonamides / diamines / Gelsemine / Diels-Alder reaction
Research Abstract

In connection with our recent report on the novel use of 2- and 4-nitrobenzenesulfonamide that provides an efficient way for the synthesis of secondary amines, we have developed 2,4-dinitrobenzenesulfonamides amine protective group, which undergo exceptionally facile and selective deprotection in the presence of 2-nitrobenzenzenesulfonamides. Combination of these sulfonamides could be used for the preparation of wide variety of diamines.
Using our protocol for the preparation of secondary amines and indole synthesis previously reported, we could achieve highly efficient total syntheses of ((]SY.+-。[))-vincadifformine and (-) -tabersonine. The common 3-indole ethanol part for both total syntheses was prepared from isonitrile, followed by introduction of acrylate moiety on the indole 2-position in one pot. Condensation of the indole part and the amine moiety protected as 2,4-dinitrobenzenesulfonamide under Mitsunobu condition gave cyclization precursors. Removal of Boc protective groups on indole NH and 2,4-dinitrosulfonamide group in mild condition furnished the desired pentacyclic skeletons via dihydrosecodine intermediate. These syntheses represents the most straightforward way to synthesize this class of compounds.
Controlling the stereochemistry of the spino-oxiindole moiety remained as a problem in the reported total syntheses of gelsemine by three groups. We could overcome this issue by the introduction of iodine substituent on the oxiindole unit and could achieve stereocontrolled total synthesis of gelsemine in racemic form. Furthermore, the key intermediate in our racemic total synthesis was synthesized as an optically active compound by asymmetric Diels-Alder reaction and Lewis acid mediated rearrangement of epoxybicyclo [2.2.1] heptene system as key reactions.

  • Research Products

    (6 results)

All Other

All Publications (6 results)

  • [Publications] Tohru Fukuyama: "Stereocontrolled Total Synthesis of (±)-Gelsemine" Journal of the American Chemical Society. 118・31. 7426-7427 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Tohru Fukuyama: "Stereocontrolled Total Synthesis of (±)-Gelsemine" Pure and Applied Chemistry. 69・3. 501-505 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Tohru Fukuyama: "2,4-Dinitrobenzenesulfonamides:A Simple and Practical Method for the Preparation of Secondary Amines and Diamines" Tetrahedron Letters. 38・33. 5831-5834 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Tohru Fukuyama, and Gang Liu: ""Stereocontrolled Total Synthesis of ((]SY.+-。[))-Gelsemine"" J.Am.Chem.Soc.118-31. 7426-7427 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Tohru Fukuyama, and Gang Liu: ""Stereocontrolled Total Synthesis of ((]SY.+-。[))-Gelsemine"" Pure Appl.Chem.69-3. 501-505 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Tohru Fukuyama, Mui Cheung, Chung-Kuang Jow, Yuko Hidai, and Toshiyuki Kan: ""2,4-Dinitrobenzenesufonamides : A Simple and Practical Method for the Preparation of a Variety of Secondary Amines and Diamines"" Tetrahedron Lett.38-33. 5831-5834 (1997)

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

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Published: 1999-03-16  

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