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Wittig rearrangement of furylmethyl ethers and application to natural product synthesis

Research Project

Project/Area Number 11672121
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemical pharmacy
Research InstitutionFaculty of Pharmaceutical Sciences, Hoshi University

Principal Investigator

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

Project Period (FY) 1999 – 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 2000: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1999: ¥1,200,000 (Direct Cost: ¥1,200,000)
KeywordsWittig rearrangement / Furfuryl ether / Chirality transfer / Ecdysone / Withanolide / Brassinolide / Steroidal side chain / Pseudopterolide / カロライドA / フラノセンブラン / フリルカルビノール / フロチルフルフリルエーテル / フリルメチルエーテル / 生理活性ステロイド / 海産性ステロイド / 合成研究
Research Abstract

Chirality transfer via the Wittig rearrangement of 2-furylmethyl ethers has been carried out. Both (2S,3Z)-and (2S,3E)-3-penten-2-yl ethers rearranged with complete chirality transfer to give (1R,2S,3E)-and (1R,2R,3E)-1-(2-furyl)-2-methyl-3-penten-1-ols, respectively.
Stereoselective construction of steroidal side chains, such as ecdysone, withanolide, and brassinolide, has been accomplished employing the Wittig rearrangement of 16-furfuryloxy steroids as a key step. Wittig rearrangement of (17E)-16α-and (17Z)-16β-furfuryloxy-6β-methoxy-3α, 5-cyclo-5α-pregn-17-enes proceeded stereoselectively to afford (20S,22S,23Z,25Z)-and (20S,22S,23Z,25Z)-23,26-epoxy-22-hydroxy-6β-methoxy-3α, 5-cyclo-27-nor-5α-cholesta-16,23,25-trienes, respectively. Steroid possessing 20S and 22S stereochemistries could be transformed into ecdysone and withanolide side chains, whereas (20S,22R)-isomer would lead to brassinolide side chain.
Studies toward the synthesis of the core of pseudopterolide have been carried out by the utilization of the intramolecular Wittig rearrangement of cyclic furfuryl ether. The key feature is the diastereoselective Wittig rearrangement of (5E)-5-methyl-3,16-dioxabicyclo [11.2.1] hexadeca-1(15), 5,13-triene providing (2R^*,3R^*)-3-isopropyl-13-oxabicyclo [8.2.1] trideca-1(12), 10-dien-2-ol with the correct stereochemistries at the C1 and C2 positions of the target molecule.

Report

(3 results)
  • 2000 Annual Research Report   Final Research Report Summary
  • 1999 Annual Research Report
  • Research Products

    (3 results)

All Other

All Publications (3 results)

  • [Publications] 津吹政可: "Asymmetric〔2,3〕Wittig rearrangement of crotyl furfuryl ethers"Tetrahedron : Asymmetry. 11. 4725-4736 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Masayoshi Tstubuki, Teruyoshi Kamata, Michiyu Nakatani, Keiko Yamazaki, Tomomi Matsui, and Toshio Honda: "Asymmetric [2,3] Wittig rearrangement of crotyl furfuryl ethers"Tetrahedron : Asymmetry. 11(23). 4725-4736 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] 津吹政可: "Asymmetric [2,3] witting rearrangement of crotyl furfuryl ethers"Tetrahedron : Asymmetry. 11(23). 4725-4736 (2000)

    • Related Report
      2000 Annual Research Report

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Published: 1999-04-01   Modified: 2016-04-21  

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