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New development of anionic [1,3] rearrangements and their application to synthesis of natural products.

Research Project

Project/Area Number 12490004
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field 広領域
Research InstitutionUtsunomiya University

Principal Investigator

SEKI Katsura  Utsunomiya University, Center for Iinstramental Analysis, Associate Professor, 機器分析センター, 助教授 (50007994)

Co-Investigator(Kenkyū-buntansha) HAGA Kazuo  Utsunomiya University, Faculty of Engineering, Associate Professor, 工学部, 助教授 (90008011)
KARIKOMI Michinori  Utsunomiya University, Faculty of Engineering, Assistant, 工学部, 助手 (00224709)
Project Period (FY) 2000 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥4,200,000 (Direct Cost: ¥4,200,000)
Fiscal Year 2002: ¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 2001: ¥2,100,000 (Direct Cost: ¥2,100,000)
Keywordsanionic [1,3] rearrangement / natural products / junicedranol / 2-thyocyanatoneopupukeanane / ptychanolide / taxol / aromatic oxy-Cope rearrangement / helicene / 天然物合成 / 機能性有機材料 / タキサン骨格 / 陰イオン促進[1,3]転位 / オキシコープ転位 / 芳香族オキシコープ転位 / 光学活性[5]ヘリセン / 不斉誘導 / テルペノイド / プチカノリド前駆体 / 骨格変換 / セスキテルペノイド / 転位反応 / 2-チオシアナトネオププケアナン / [1,3]転位反応 / oxy-Cope転位反応
Research Abstract

Natural products possess various kinds of carbon skeletons and the development of the efficient preparation methods for these carbon skeletons is one of very important subjects in organic synthesis. In the course of our studies on the synthesis of natural products, we have already investigated the practical methods for the conversion of bridged bicyclic compounds into [m-n] fused-ring compounds, using an anionic [1,3] rearrangement as a key step. We attempted the total synthesis of (±)-junicedranol, a marine sesquiterpene-alcohol with a unique tricycliic skeleton, using the anionic [1,3] rearrangement followed by the Diels-Alder reaction strategy in order to elucidate the synthetic utility of the rearrangement, Moreover, (±)-2-thiocyanatoneopupukeanane, a marine sesquiterpene-thiocyanate with a tricyclo[4.3.1.0^<3,7>]decane skeleton, was prepared through a pinacol-type rearrangement of a bicyclo[2.2.2]oct-5-en-2-ol giving a bicyclo[3.2.1]oct-6-en-2-one derivative and an aldol reaction … More leading to the neopupukeanane framework.
We have also developed a novel methodology for the construction of unique diquinanes, possessing four contiguous methyl groups on their convex, by employing a combination of pinacol-type rearrangement and the anionic [1,3] rearrangement. This stratergy would be applicable to the total synthesis of natural diquinanes, such as ptychanolide and its related compounds. An efficient one-pot synthesis of a 10,10-ethylenebicyclo[5.2.1]dec-8-ene-4-one derivative, which can be considered as a synthetic intermediate for the taxane skelton, has been achieved by tandem anionic [1,3] and oxy-Cope rearrangements of 2-vinylbicyclo[3.2.1] oct-6-en-2-ol.
On the other hand, we have previously reported an efficient anionic [3,3] rearrangement of bridged compounds containing a 1-aryl-3-butenol unit, so-called aromatic oxy-Cope rearrangement. We have then developed a novel synthesis of 2-acetoxy[5]helicene, using this aromatic oxy-Cope rearrangement as a key step. In addtion, this strategy has been applied to a practicall method for the the synthesis of chiral [5]helicenes. The carbonyl groups of the above intermediates can be easily converted to other functional groups, so that these compounds are useful for further synthetic studies of chiral hedical compounds possessing a variety of functionalities. Application of this trategy to the synthesis of other hedical systems are under investigation. Less

Report

(4 results)
  • 2002 Annual Research Report   Final Research Report Summary
  • 2001 Annual Research Report
  • 2000 Annual Research Report
  • Research Products

    (18 results)

All 2003 2002 2001 2000 Other

All Journal Article (12 results) Publications (6 results)

  • [Journal Article] Synthesis of chiral [5]helicenes using aromatic oxy-Cope rearrangement as a key step2003

    • Author(s)
      Y.Ogawa, M.Toyama, M.Karikomi, K.Seki, K.Haga, T.Uyehara
    • Journal Title

      Tetrahedron Letters 44・10

      Pages: 2167-2170

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Journal Article] Synthesis of chiral [5]helicenes using oxy-Cope rearrangement as a key step2003

    • Author(s)
      Y.Ogawa
    • Journal Title

      Tetrahedron Letters 44(10)

      Pages: 2167-2170

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Journal Article] A novel method for the synthesis of diquinanes based on anionic [1,3] rearrangement of bicyclo[3. 2. 1]oct-6-en-2-ols2002

    • Author(s)
      H.Hashimoto, Y.Abe, Y.Mayuzumi, M.Karikomi, K.Seki, K.Haga, T.Uyehara
    • Journal Title

      Tetrahedron Letters 43・2

      Pages: 265-267

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Journal Article] Synthetic study of bicyclo[5.2.1]dec-8-en-4-ones based on tandem anionic [1,3] and oxy-Cope rearrangements of 2-vinylbicyclo [3. 2. 1]oct-6-en-2-ols2002

    • Author(s)
      H.Hashimoto, T.Jin, M.Karikomi, K.Seki, K.Haga, T.Uyehara
    • Journal Title

      Tetrahedron Letters 43・20

      Pages: 3633-3636

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Journal Article] Synthesis of 2-acetoxy[5]helicene by sequential double aromatic oxy-Cope rearrangement2002

    • Author(s)
      Y.Ogawa, T.Ueno, M.Kayikomi, K.Seki, K.Haga, T.Uyehara
    • Journal Title

      Tetrahedron Letters 43・43

      Pages: 7827-7829

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Journal Article] A novel method for the synthesis of diquinanes based on anionic [1,3] rearrangement of bycyclo[3.2.1]oct-6-en-2-ols2002

    • Author(s)
      H.Hashimoto
    • Journal Title

      Tetrahderon Letters 43(2)

      Pages: 265-267

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Journal Article] Synthetic study of bycyclo[5.2.1]dec-8-en-4-ones based on tandem anionic [1,3] and oxy-Cope rearrangement of 2-vinybicyclo[3.2.1]oct-6-en-2-ols2002

    • Author(s)
      H.Hashimoto
    • Journal Title

      Tetrahedron Letters 43(20)

      Pages: 3633-3636

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Journal Article] Synthesis of 2-actoxy[5]helicene by sequential double aromatic oxy-Cope rearrangement2002

    • Author(s)
      Y.Ogawa
    • Journal Title

      Tetrahedron Letters 43(43)

      Pages: 7827-7829

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Journal Article] The first total synthesis of (±)-2-thiocyanatoneopupukeanane based on a pinacol-type rearrangement.2001

    • Author(s)
      T.Uyehara, Y.Sato, H.Ishizuka, Y.Sakiyama, M.Ueno, T.Sato
    • Journal Title

      Tetrahedron Letters 42・4

      Pages: 699-702

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Journal Article] The first total synthesis of (±)-2-thiocyanatoneopupukeanane based on a pinacol-type rearrangement2001

    • Author(s)
      T.Uyehara
    • Journal Title

      Tetrahedron Letters 42(4)

      Pages: 699-702

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Journal Article] The first total synthesis of (±)-junicedranol based on a novel anionic [1, 3] rearrangement2000

    • Author(s)
      I.Uyehara, Y.Sato, H.Ishizuka, Y.Sakiyama, M.Ueno, T.Sato
    • Journal Title

      Tetrahedron Letters 41・12

      Pages: 1939-1942

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Journal Article] The first total synthesis of (±)-junicedranol based on a novel anionic [1,3] rearrangement2000

    • Author(s)
      T.Uyehara
    • Journal Title

      Tetrahedron Letters 41(12)

      Pages: 1939-1942

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] H.Hashimoto, T.Jin, M.Karikomi, K.Seki, K.Haga, T.Uyehara: "Synthetic study of bicyclo[5.2.1]dec-8-en-4-ones based on tandem anionic [1,3] and oxy-Cope rearrangements of 2-vinylbicyclo[3.2.1]oct-6-en-2-ols"Tetrahedron Letters. 43・20. 3633-3636 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Y.Ogawa, T.Ueno, M.Karikomi, K.Seki, K.Haga, T.Uyehara: "Synthesis of 2-acetoxy[5]helicene by sequential double aromatic oxy-Cope rearrangement"Tetrahedron Letters. 43・43. 7827-7829 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Y.Ogawa, M.Toyama, M.Karikomi, K.Seki, K.Haga, T.Uyehara: "Synthesis of chiral [5]helicenes using aromatic oxy-Cope rearrangement as a key step"Tetrahedron Letters. 44・10. 2167-2170 (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] H. Hashimoto, Y. Abe, Y. Mayuzumi, M. Karikomi, K. Seki, K. Haga, T. Uyehara: "A novel method for the synthesis of diquinanes based on anionic [1,3] rearrangement of bicyclo[3.2.1]oct-6-en-2-ols"Tetrahedron Letters. 43・2. 265-267 (2002)

    • Related Report
      2001 Annual Research Report
  • [Publications] Tadao Uyehara: "The first total synthesis of (±)-junicedranol based on a novel anionic [1,3] rearrangement"Tetrahedron Letters. 41. 1939-1942 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Tadao Uyehara: "The first total synthesis of (±)-2-thiocyanatoneopupukeanane based on a pinacol-type rearrangement"Tetrahedron Letters. 42. 699-702 (2001)

    • Related Report
      2000 Annual Research Report

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

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