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Studies on the synthesis of physiologically active furanocembrane derivatives

Research Project

Project/Area Number 13672238
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemical pharmacy
Research InstitutionHoshi University

Principal Investigator

TSUBUKI Masayoshi  Hoshi University, Faculty of Pharmaceutical Sciences, Associate Professor, 薬学部, 助教授 (90163865)

Project Period (FY) 2001 – 2003
Project Status Completed (Fiscal Year 2003)
Budget Amount *help
¥2,900,000 (Direct Cost: ¥2,900,000)
Fiscal Year 2003: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 2002: ¥900,000 (Direct Cost: ¥900,000)
Fiscal Year 2001: ¥1,100,000 (Direct Cost: ¥1,100,000)
KeywordsCyclic furfuryl ether / Wittig rearrangement / Furanocembrane / Kallolide A / Bipinnatin J / Pinnatin A / Cyclopropanation / Cross-coupling / Stilleクロスカップリング / γ-ブテノリド / グリセルアルデヒド / ゲルソラン / フラノジテルペン / 鈴木クロスカップリング / Witting転位 / シュードプテラン
Research Abstract

A stereocontrolled synthesis of anti-and syn-β-isopropenyl alcohol moieties at the C(2)-C(3) positions of kallolide A and pinnatin A was accomplished employing the [2,3] Wittig rearrangement of (E)-and (Z)-cyclic furfuryl ethers. Both (5E)-and (5Z)-5,15-dimethyl-3,16-dioxabicyclo [11.2.1] hexadeca-1(15),5,13-trienes rearranged with high diastereoselectivity to give (2R^*,3R^*)-and (2R^*,3S^*)-3-isopropenyl-12-methyl-13-oxabicyclo[8.2.1]trideca-1(12), 10-dien-2-ols, respectively. Enantioselective Wittig rearrangement of (E)-and (Z)-furfuryl ethers using butyllithium and a chiral bis(oxazoline) was also examined to provide (2R, 3R)-homoallylic alcohol in up to 61% ee and (2R, 3S)-alcohol in up to 93% ee, respectively.
A stereoselective synthesis of the cyclopropylfuran unit in pinnatin A was carried out. Cyclopropanation of vinylfuroate gave desired cycloporpylfuroate, albeit in low yield. Suzuki cross-coupling of cyclopropylboronic acid with bromofuroate afforded the corresponding (1R, 2R, 2'S)-5-[2-(1,4-dioxaspiro[4.5]decan-2'-yl)-2-methylcyclopropyl]-3-methyl-2-furoic acid methyl ester in 77% yield. This compound was converted into aldehyde, a key intermediate for the synthesis of pinnatin A. Chiral synthesis of the core structure of bipinnatin J was investigated. Stille cross-coupling of tributylstannylfuran with (Z)-bromoalkene gave (S, Z)-1-(5-tert-butyldimethylsiloxymethyl-4-methyl-2-furyl)-2-methyl-4,5-O-(p-methoxybenzylidene)-1-pentene stereoselectively. Ru-catalyzed cyclic carbonylation of allenyl alcohol afforded γ-lactone, (S, 1E, 5Z, 9E)-1-bromo-11-tert-butyldimethylsiloxy-4-hydroxy-2,10-dimethylundeca-1,5,9-triene-6-carboxylic acid lactone.

Report

(4 results)
  • 2003 Annual Research Report   Final Research Report Summary
  • 2002 Annual Research Report
  • 2001 Annual Research Report
  • Research Products

    (6 results)

All Other

All Publications (6 results)

  • [Publications] M.Tsubuki et al.: "Stereoselective Construction of a β-Isopropenyl Alcohol Moiety at the C(2) and (3) of Kallolide a and Pinnatin a Using a [2,3] Wittig Rearrangement of Cyclic Furfuryl Ethers"The Journal of Organic Chemistry. 68・26. 10183-10186 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] H.F.Kasai, M.Tsubuki et al.: "Separation of stereoisomers of several furan derivatives by capillary gas chromatography-mass spectrometry, supercritical fluid chromatography, and liquid chromatography using chiral stationary phases"Journal of Chromatography A. 977・1. 125-134 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Masayoshi Tsubuki, Kazunori Takahashi, Toshio Honda: "Stereoselective Construction of a β-Isopropenyl Alcohol Moiety at the C(2) and (3) of Kallolide A and Pinnatin A Using a [2,3] Wittig Rearrangement of Cyclic Furfuryl Ethers"J.Org.Chem.. 68(26). 10183-10186 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] Hiroko F.Kasai, Masayoshi Tsubuki, Kazunori Takahashi, Mika Shirao, Yoichiro Matsumoto, Toshio Honda, Yoshiyuki Seyama: "Separation of stereoisomers of several furan derivatives by capillary gas chromatograpy-mass spectrometry, supercritical fluid chromatograpy, and liquid chromatograpy using chiral stationary phases"J.Chromatogr.A. 977(1). 125-134 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2003 Final Research Report Summary
  • [Publications] M.Tsubuki, et al.: "Stereoselective Construction of a β-Isopropenyl Alcohol Moiety at the C(2)---"The Journal of Organic Chemistry. 68・26. 10183-10186 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] H.F.Kasai, M.Tsubuki, et al.: "Separation of stereoisomers of several furan derivatives by capillary gas-----"Journal of Chromatography A. 977・1. 125-134 (2002)

    • Related Report
      2002 Annual Research Report

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Published: 2001-04-01   Modified: 2016-04-21  

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