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Development of Synthetic Methods for the Silaallene Cationic Species and the Related Compounds and Their Application Reactions

Research Project

Project/Area Number 16390008
Research Category

Grant-in-Aid for Scientific Research (B)

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

Principal Investigator

NAGAO Yoshimitsu  The University of Tokushima, Graduate School, Institute of Health Biosciences, Professor, 大学院ヘルスバイオサイエンス研究部, 教授 (40027074)

Co-Investigator(Kenkyū-buntansha) SANO Shigeki  The University of Tokushima, Graduate School, Institute of Health Biosciences, Associate Professor, 大学院ヘルスバイオサイエンス研究部, 助教授 (20226038)
Project Period (FY) 2004 – 2006
Project Status Completed (Fiscal Year 2006)
Budget Amount *help
¥14,500,000 (Direct Cost: ¥14,500,000)
Fiscal Year 2006: ¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 2005: ¥5,000,000 (Direct Cost: ¥5,000,000)
Fiscal Year 2004: ¥7,700,000 (Direct Cost: ¥7,700,000)
Keywordssilaallene / diarylmonoalkynylfluorosilane / dialkynyldiarylsilane / oxasiletane / azasiletane / silacyclobutene / desilylation / conjugated diene / シラレン / シラアレンカチオン / ジアリルアルキニルフルオロシラン / ジアリルジアルキニルシラン / テトラクロロシラン / ジアリルジフルオロシラン / X線結晶構造解析 / テトラフルオロシラン / アリルトリクロロシラン / ジアリルジクロロシラン
Research Abstract

First, we have developed highly efficient synthetic methods for diarylmonoalkynylfluorosilanes and dialkynyldiarylsilanes as follows. Reaction of aryllithiums with tetrachlorosilane gave monoaryltrichlorosilanes, which were treated with other aryllithiums to afford diaryldichlorosilanes. After halogen exchange reaction (Cl→F), treatment of the resulting diaryldifluorosilanes with alkynyllithiums gave the desired diarylmonoalkynylfluorosilanes. Their similar reactions with other alkynyllithiums furnished the corresponding alkynyl-substituted dialkynyldiarylsilanes in excellent yields. Treatment of the monoalkynylmonoarylfluorosilane bearing t-Bu, Tip, phenylalkynyl, and fluorine atom with t-BuLi at 0℃ and then at room temperature or under reflux generated a 1-silaallene. The 1-silaallene was in situ allowed to react with ketones, aldehydes, and an imine to give the corresponding 1,2-oxasiletanes and 1,2-azasiletane, respectively. Treatment of the differrent kinds of alkynyl-substituted dialkynyldiarylsilanes with biscyclopentadienylzirconocene-ethylene complex followed by acidification with 3N HC1 gave regio-and stereoselectively the corresponding silacyclobutenes in good yields. Desilylation of the silacyclobutenes with tetrabutylammonium fluoride afforded stereoselectively unsymmetrical conjugated dienes and trienes in excellent yields, respectively.

Report

(4 results)
  • 2006 Annual Research Report   Final Research Report Summary
  • 2005 Annual Research Report
  • 2004 Annual Research Report
  • Research Products

    (17 results)

All 2006 2005 2004 Other

All Journal Article (17 results)

  • [Journal Article] Synthesis of Novel Silacyclobutene Derivatives Utilizing Zirconocene-and Titanocene-Ethylene Complexes2006

    • Author(s)
      Yoshimitsu Nagao
    • Journal Title

      Heterocycles 70

      Pages: 71-75

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Annual Research Report 2006 Final Research Report Summary
  • [Journal Article] Expeditious Syntheses of Conjugated Allenyl Esters and Oxazoles through a Cascade Reaction of α-Alkynyl Malonates under Alkaline Conditions2006

    • Author(s)
      Yoshimitsu Nagao
    • Journal Title

      Chemical & Pharmaceutical Bulletin 54・2

      Pages: 196-203

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Synthesis of Novel Silacyclobutene Derivatives Utilizing Zirconocene-and Titanocene-Ethylene Complexes2006

    • Author(s)
      Yoshimitsu Nagao et al.
    • Journal Title

      Heterocycles 70

      Pages: 71-75

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Expeditious Syntheses of Conjugated Allenyl Esters and Oxazoles through a Cascade Reaction of a-Alkynyl Malonates under Alkaline Conditions2006

    • Author(s)
      Yoshimitsu Nagao et al.
    • Journal Title

      Chemical & Pharmaceutical Bulletin 54(2)

      Pages: 196-203

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Expeditious Syntheses of Conjyugated Allenyl Esters and Oxazoles through a Cascade Reaction of α-Alkynyl Malonates under Alkaline Conditions2006

    • Author(s)
      Yoshimitsu Nagao
    • Journal Title

      Chemical & Pharmaceutical Bulletin 54・2

      Pages: 196-203

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Trimethylaluminium-Induced Diastereoselective Methylation onto Ethyl 2-Oxocyclopentane-1-carboxylate and Isomerization between Both of the Dimethylaluminium-Alkoxide Products2005

    • Author(s)
      Yoshimitsu Nagao
    • Journal Title

      Tetrahedron Letters 46・16

      Pages: 2887-2891

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary 2005 Annual Research Report
  • [Journal Article] Facile Generation Method for Conjugated Allenyl Esters Based on retro-Dieckmann Type Ring-Opening2005

    • Author(s)
      Yoshimitsu Nagao
    • Journal Title

      Tetrahedron Letters 46・16

      Pages: 2883-2886

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary 2005 Annual Research Report
  • [Journal Article] Trimethylaluminium-Induced Diastereoselective Methylation onto Ethyl 2- Oxocyclopentane-1-carboxylate and Isomerization between Both of the Dimethylaluminium-Alkoxide Products2005

    • Author(s)
      Yoshimitsu Nagao et al.
    • Journal Title

      Tetrahedron Letters 46(16)

      Pages: 2887-2891

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Facile Generation Method for Conjugated Allenyl Esters Based on retro-Dieckmann Type Ring-Opening2005

    • Author(s)
      Yoshimitsu Nagao et al.
    • Journal Title

      Tetrahedron Letters 46(16)

      Pages: 2883-2886

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] New Synthetic Methods for Seven- and Eight-Membered Cyclic Ethers Based on the Ring-Expansion Reactions of Hydroxy or Lithioxy Methoxyallenylisochroman Derivatives2004

    • Author(s)
      Yoshimitsu Nagao
    • Journal Title

      Synlett 3

      Pages: 481-484

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] New Synthetic Methods for Seven-and Eight-Membered Cyclic Ethers Based on the Ring-Expansion Reactions of Hydroxy or Lithioxy Methoxyallenylisochroman Derivatives2004

    • Author(s)
      Yoshimitsu Nagao et al.
    • Journal Title

      Synlett 3

      Pages: 481-484

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] New Synthetic Methods for Seven-and Eight-Membered Cyclic Ethers Based on the Ring-Expansion Reactions of Hydroxy or Lithioxy Methoxyallenylisochroman Derivatives2004

    • Author(s)
      Yoshimitsu Nagao
    • Journal Title

      Synlett 3

      Pages: 481-484

    • Related Report
      2004 Annual Research Report
  • [Journal Article] New Ring-Expansion Reactions of Hydroxy Propenoyl Cyclic Compounds under Palladium(0)/Phosphine-Catalyzed Conditions2004

    • Author(s)
      Yoshimitsu Nagao
    • Journal Title

      Org.Lett. 6

      Pages: 2133-2136

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Preferential Conformation of the Six-membered Cyclic Compounds Bearing Both Trimethyl-siloxy(or Methoxymethyleneoxy) and Tributyistannyl Groups at the Geminal Position2004

    • Author(s)
      Yoshimitsu Nagao
    • Journal Title

      Heterocycles 62

      Pages: 229-234

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Intramolecular Nonbonded S…O Interaction in Acetazolamide and Thiadiazolinethione Molecules in Their Dimeric Crystalline Structures and Complex Crystalline Structures with Enzymes2004

    • Author(s)
      Yoshimitsu Nagao
    • Journal Title

      Tetrahedron Letters 45

      Pages: 8757-8761

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Stereoselective Synthesis of Unsymmetrical Conjugated Dienes and Trienes Utilizing Silacyclobutenes

    • Author(s)
      Yoshimitsu Nagao
    • Journal Title

      Tetrahedron Letters (in press)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Stereoselective Synthesis of Unsymmetrical Conjugated Dienes and Trienes Utilizing Silacyclobutenes

    • Author(s)
      Yoshimitsu Nagao et al.
    • Journal Title

      Tetrahedron Letters (in press)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary

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Published: 2004-04-01   Modified: 2016-04-21  

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