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Development of Versatile Chiral Building Blocks from Meso-Enediol Compounds Utilizing Catalytic Asymmetrization Reactions

Research Project

Project/Area Number 09672134
Research Category

Grant-in-Aid for Scientific Research (C)

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

Principal Investigator

HIROYA Kou  Tohoku University, Graduate School of Pharmaceutical Sciences, Associated Professor, 大学院・薬学研究科, 助教授 (70192721)

Project Period (FY) 1997 – 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2000: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1999: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1998: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 1997: ¥1,400,000 (Direct Cost: ¥1,400,000)
Keywordschiral building block / cationic rhodium complex / enantioselective synthesit / (-)-shikimic acid / (-)-quinic acid / (-)-zeylenol / (-)-tonkinenin A / (-)-qvarigranol G / キラル-4-オキシシクロヘキセノン / 触媒 / 不斉配位子 / 光学分割 / シリルエーテル / (+)-pipoxide / (-)-epizeylenol / キラル4-オキシシクロヘキセノン / キナ酸 / シキミ酸 / コンベックス面選択性 / 逆ディールス・アルダー反応 / ヒドロキシル化反応 / 触媒的不斉化 / キラルBINAPロジウム触媒 / 天然物合成 / エナンチオ制御御合成 / キラルシクロヘキセノン / メソ化合物
Research Abstract

The asymmetric olefin migration reaction catalyzed by cationic Rh-complex ligated with chiral BINAP had been successfully carried out for the meso type enediol silyl ether having bicyclo [2.2.1] ring system in its background and 7-membered ring system as substrates. However, applications of this reaction to the other simplified meso substrates (e.g.8-membered ring substrate or 6-membered ring substrates) did not gave satisfactory results. Therefore, the requirement to afford high selectivity of this asymmetric olefin migration reaction was suggested that at least some bulky ether subtituents are necessary at the both allylic positions.
On the other hand, keto-silyl ether having high optical purity obtained by this methodology was applied to natural products syntheses. As a result, (-)-malyngolide, (-)-shikimic acid, (-)-quinic acid, (-)-zeylenol, (+)-pipoxide, (-)-uvarigranol G, (-)-isoretronecanl, (+)-trachelanthamidine, and two kinds of cyclohexenone derivatives could be synthesized as the optically active form. Furthermore, the proposed structure of (-)-tonkinenin A could be revised and (-)-epizeylenol could be disproved.

Report

(5 results)
  • 2000 Annual Research Report   Final Research Report Summary
  • 1999 Annual Research Report
  • 1998 Annual Research Report
  • 1997 Annual Research Report
  • Research Products

    (28 results)

All Other

All Publications (28 results)

  • [Publications] Hiroyuki Konno: "A New Tactic for Diastereo-and Enantiocontrolled Synthesis of (-)-Malyngolide via Catalytic Meso-Asymmetrization."Tetrahedron Lettes. 38・35. 6032-6026 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Masanori Saito: "First Enantiocontrolled Syntheses of (+)-Ulein and (+)-Dasycarpidone."Chemical Communications. 8. 765-766 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Kou Hiroya: "A Concise Enantio-and Diastereo-controlled Synthesis of (-)-Quinic Acid and (-)-Shikimic Acid."Chemical Communications. 18. 2033-2034 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Hiroyuki Konno: "An Enantio-and Diastereoselective Synthesis of (-)-Isoretronecanol and (+)-Trachelanthamidine from a Meso Precursor."Heterocycles. 49・1. 33-37 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Kou Hiroya: "The First Enantiocontrolled Synthesis of Naturally Occurring Polyoxygenated Cyclohexenylmethanol Dibenzoates, (-)-Zeylenol, (-)-Uvarigranol G, (-)-Tonkinenin A and (+)-Pipoxide."Chemical Communications. 21. 2197-2198 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Kou Hiroya: "Preparation of the Synthetic Equivalents of Chiral Cyclohexadienone and Cycloheptadienone : The Enantio-and Diastereo-controlled Synthesis of (-)-Clavularin B."Synlett. 5. 529-532 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Masatoshi Honzumi: "Integrated Synthesis of Conduritols A-F Using a Single Chiral Building Block."Chemical Communications. 19. 1985-1986 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Hiromi Nakajima: "A Stereocontrolled Route to (-)-Epibatidine Using A Chiral cis-Cyclohexadiene-1, 4-diol Equivalent."Synlett. 9. 1405-1406 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Kou Hiroya: "Total Syntheses of Three Natural Products, Vignafuran, 2-(4-Hydroxy-2-methoxyphenyl)-6-methoxybenzofuran-3-carboxylic Acid Methyl Ester, and Coumestrol from a Common Starting Material."Journal of the Chemical Society, Perkin Transactions 1. 24. 4339-4346 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Hiroyuki Konno: "A New Tactic for Diastereo- and Enantiocontrolled ISynthesis of (-)-Malyngolide via Catalytic Meso-Asymmetrization."Tetrahedron Letters. 38. 6032-6026 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Masanori Saito: "First Enantiocontrolled Syntheses of (+)-Ulein and (+)-Dasycarpidone."Chemical Communications. 765-766 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Kou Hiroya: "A Concise Enantio- and Diastereo-controlled Synthesis of (-)-Quinic Acid and (-)-Shikimic Acid."Chemical Communications. 2033-2034 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Hiroyuki Konno: "An Enantio- and Diastereoselective Synthesis of (-)-Isoretronecanol and (+)-Trachelanthamidine from a Meso Precursor."Heterocycles. 49. 33-37 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Kou Hiroya: "The First Enantiocontrolled Synthesis of Naturally Occurring Polyoxygenated Cyclohexenylmethanol Dibenzoates, (-)-Zeylenol, (-)-Uvarigranol G,(-)-Tonkinenin A and (+)-Pipoxide."Chemical Communications. 2197-2198 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Kou Hiroya: "Preparation of the Synthetic Equivalents of Chiral Cyclohexadienone and Cycloheptadienone : The Enantio- and Diastereo-controlled Synthesis of (-)-Clavularin B."Synlett. 529-532 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Masatoshi Honzumi: "Integrated Synthesis of Conduritols A-F Using a Single Chiral Building Block."Chemical Communications. 1985-1986 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Hiromi Nakashima: "A Stereocontrolled Route to (-)-Epibatidine Using a Chiral cis-Cyclohexadiene-1,4-diol Equivalent."Synlett. 1405-1406 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Kou Hiroya: "Total Syntheses of Three Natural Products, Vignafuran, 2-(4-Hydroxy-2-methoxyphenyl)-6-methoxybenzofuran-3-carboxylic Acid Methyl Ester, and Coumestrol from a Common Starting Material."Journal of the Chemical Society, Perkin Transactions 1. 4339-4346 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Kou Hiroya: "Total syntheses of three natural products, vignafuran,2-(4-hydroxy-2-methoxyphenyl)-6-methoxy-benzofuran-3-carboxylic acd methyl ester, and coumestrol from a common starting material."Journal of Chemical Society, Perkin Transactions 1. 4339-4346 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Kou Hiroya: "Preparation of the Synthetic Equivalents of Chiral Cyclohexadienone and Cycloheptadienone :The Enantio- and Diastereo-controlled Synthesis of (-)-Clavularin B"Synlett. 5. 529-532 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Hiromi Nakajima: "A Stereocontrolled Route to (-)-Epibatidine Using A Chiral cis-Cyclohexadiene-1,4-diol Equivalent"Synlett. 9. 1405-1406 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Masatoshi Honzumi: "Integrated Synthesis of Conduritols A-F Using a Single Chiral Buiding Block"Chemical Communications. 19. 1985-1986 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Kou Hiroya: "The First Enantiocontrolled Synthesis of Naturally Occurring Polyoxygenated Cyclohexenylmethanol Dibenzoates, (-)-Zeylenol, (-)-Uvarigranol G, (-)-Tonkinenin A and (+)-Pipoxide"Chemical Communications. 21. 2197-2198 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Kou Hiroya: "An Enantio-and Diastereoselective Synthesis of (-)-Isoretronecanol and (+)-Trachelanthamidine from A Meso Precursor" Heterocycles. 49. 33-37 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Kou Hiroya: "A Concise Enantio-and Diastereo-controlled Synthesis of (-)-Quinic Acid and (-)-Shikimic Acid" Chemical Communications. 2033-2034 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Kou Hiroya: "Preparation of the Synthetic Equivalnets of Chiral Cyclohexadienone and Cycloheptadienone : The Enantio and Diastereo-controlled Synthesis of (-)-Clavularin B" SYNLETT. 印刷中. (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] Kou Hiroya: "A New Tactic for Diastereo-and Enantiocontorolled Synthesis of (-) -Malyngolide via Catalytic Meso-Asymmetrization" Tetrahedron Lett.38 (34). 6023-6026 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Kou Hirata: "An Enantio-and Diastereoselective Synthesis of (-) -Isoretronecanol and (+) -Trachelanthamidine from A Meso Precursor" Heterocycles. (印刷中). (1998)

    • Related Report
      1997 Annual Research Report

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Published: 1997-04-01   Modified: 2016-04-21  

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