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New Guanidine Chemistry

Research Project

Project/Area Number 14370717
Research Category

Grant-in-Aid for Scientific Research (B)

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

Principal Investigator

ISHIKAWA Tsutomu  Chiba University, Graduate School of Pharmaceutical Sciences, Professor, 大学院・薬学研究院, 教授 (20114233)

Co-Investigator(Kenkyū-buntansha) WATANABE Toshiko  Chiba University, Graduate School of Pharmaceutical Sciences, Associate Professor, 大学院・薬学研究院, 助教授 (40120323)
SEKI Hiroko  Chiba University, Chemical Analytical Center, Associate Professor, 分析センター, 助教授 (60114245)
Project Period (FY) 2002 – 2004
Project Status Completed (Fiscal Year 2004)
Budget Amount *help
¥10,600,000 (Direct Cost: ¥10,600,000)
Fiscal Year 2004: ¥1,900,000 (Direct Cost: ¥1,900,000)
Fiscal Year 2003: ¥2,700,000 (Direct Cost: ¥2,700,000)
Fiscal Year 2002: ¥6,000,000 (Direct Cost: ¥6,000,000)
Keywordsguanidine / chiral catalyst / guanidinium ylide / aziridine / aldehyde / asymmetric synthesis / building block / グアニジニウム塩 / ビニルアルデヒド / スフィンゴシン / キラルグアニジン / 反応機構 / エポキシド / 環開裂 / 還元的開裂 / キラル / ネーバー反応 / β-ラクタム
Research Abstract

Guanidinium ylide-paiticipated asymmetric aziridination was precisely examined. Thus, the formation of the ylides was confirmed by NMR spectroscopy. Acid anhydrides, like silica gel, could contribute to the fragmentation of adduct intermediates from guanidinium ylides and aryl aldehydes to aziridine and urea products. Examination of reaction using a variety of p-substituted benzaldehydes allowed us to categorize the aziridination to two groups dependent upon the substituents, causing different reaction rate and stereochemistry of aziridine products. The enatio-and diastereoselectivities could be reasonably explained by Hammett analysis.
This aziridine synthesis is sensitive to the steric bulikiness of the stalling guanidinium salts and, thus, low reactivity was observed on substituted guanidinium salts. α,β-Unsaturated aldehydes, like aryl aldehydes, could serve as aldehyde substrates to afford aziridines with high enantioselectivity. Straight-forward aziridine formation was observed when tertiary guanidine are subjected to not only the reaction in the presence of alkylating agents but also the reaction with styrene oxides.
On the other hand in the course of exploiting the potential functionality of chiral guanidines guanidine-catalyzed asymmetric chromanone construction was examined by application of intramolecular Michael reaction expected asymmetric induction was observed. General preparation method for the polymer-supported guanidines as potential environment-directed catalysts was basically established. Atom-economical synthesis of biologically active N-containing compounds using chiral aziridines as building blocks was developed. Thus, ring-opening reactions of aziridine skeletons were examined either under reductive conditions or in the presence of nucleophiles. As a example enantioselective total synthesis of D-erythro-sphingosine was achieved. Furthermore, chemical modification of aziridines was attempted for their ring-expansion to β-lactam skeletons

Report

(4 results)
  • 2004 Annual Research Report   Final Research Report Summary
  • 2003 Annual Research Report
  • 2002 Annual Research Report
  • Research Products

    (24 results)

All 2005 2004 2003 2002 Other

All Journal Article (16 results) Patent(Industrial Property Rights) (2 results) Publications (6 results)

  • [Journal Article] o-Bisguanidinobenzene, a Powerful Hydrogen Acceptor : Crystal Structures of Organic Complexes with Benzoic Acid, Phenol, and Benzyl Alcohol2005

    • Author(s)
      M.Kawahata, K.Yamaguchi, T.Ishikawa
    • Journal Title

      Crystal Growth & Design 5

      Pages: 373-377

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Mechanistic Approaches to Asymmetric Synthesis of Aziridines from Guanidinium Ylides and Aryl Aldehydes2005

    • Author(s)
      T.Haga, T.Ishikawa
    • Journal Title

      Tetrahedron 61

      Pages: 2857-2869

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Annual Research Report 2004 Final Research Report Summary
  • [Journal Article] Polymer-supported and Polymeric Chiral Guanidiens : Preparation and Application to the Asymmetric Michael Reaction of Iminoacetate with Methyl Vinyl Ketone2005

    • Author(s)
      D.Wannaporn, T.Ishikawa
    • Journal Title

      Molecular Diversity (in press)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] o-Bisguanidinobenzene, a Powerful Hydrogen Acceptor : Crystal Structures of Organic Complexes with Benzoic Acid, Phenol, and Benzyl Alcohol2005

    • Author(s)
      M.Kawahata, K.Yamaguchi, T.Ishikawa
    • Journal Title

      Cryst.Grow.Desgin 5

      Pages: 373-377

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Polymer-supported and Polymeric Chiral Guanidiens : Preparation andApplication to the Asymmetric Michael Reaction of Iminoacetate with Methy1 Viny1 Ketone2005

    • Author(s)
      D.Wannaporn, T.Ishikawa
    • Journal Title

      Molecular Deversity (in press)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Structural Revision of the Ring-Opened Product in the ZnCl_2-Catalyzed Reactions of 1-Benzyl-2-phenylaziridine with Thiols2004

    • Author(s)
      Y.Furuta, T.Kumamoto, T.Ishikawa
    • Journal Title

      Synlett

      Pages: 362-364

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Guanidines as a Nitrogen Source for Direct Conversion of Epoxides to Aziridines2004

    • Author(s)
      Y.Tsuchiya, T.Kumamoto, T.Ishikawa
    • Journal Title

      Journal of Organic Chemistry 69

      Pages: 8504-8505

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Guanidines as a Nitrogen Source for Direct Conversion of Epoxides to Aziridine2004

    • Author(s)
      Y.Tsuchiya, T.Kumamoto, T.Ishikawa
    • Journal Title

      J.Org.Chem. 69

      Pages: 8504-8505

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Structural Revision of the Ring-Opened Product in the ZnCl_2-Catalyzed Reactions of 1-Benzyl-2-phenylaziridine with Thiols2004

    • Author(s)
      Y.Furuta, T.Kumamoto, T.Ishikawa
    • Journal Title

      Synlett 2号

      Pages: 362-364

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Guanidines as a Nitrogen Source for Direct Conversion of Epoxides to Aziridiens2004

    • Author(s)
      Y.Tsutiya, T.Kumamoto, T.Ishikawa
    • Journal Title

      J.Org.Chem. 69巻

      Pages: 8504-8505

    • Related Report
      2004 Annual Research Report
  • [Journal Article] グアニジン型キラル補助剤2003

    • Author(s)
      石川 勉, 磯部敏男
    • Journal Title

      有機合成化学協会誌 61

      Pages: 59-66

    • NAID

      10011904428

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Chiral Guanidines2003

    • Author(s)
      T.Ishikawa, T.Isobe
    • Journal Title

      J.Syn.Org.Chem.Jpn 61

      Pages: 59-66

    • NAID

      10011904428

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Guanidine-Assisted Asymmetric Synthesis2002

    • Author(s)
      T.Ishikawa, T.Isobe
    • Journal Title

      Chemistry : European Journal 8

      Pages: 552-557

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] ニューグアニジンケミストリー-機能性の発掘を目指して-2002

    • Author(s)
      石川 勉
    • Journal Title

      ファルマシア 38

      Pages: 505-507

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Guanidine-Assisted Asymmetric Synthesis2002

    • Author(s)
      T.Ishikawa, T.Isobe
    • Journal Title

      Chem.Eur.J. 8

      Pages: 552-557

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] New Guanidine Chemistry-Toward Potential functions-2002

    • Author(s)
      T.Ishikawa
    • Journal Title

      Farumashia 38

      Pages: 505-507

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Patent(Industrial Property Rights)] ビスグアニジン型化合物2004

    • Inventor(s)
      石川 勉, 川幡 正敏
    • Industrial Property Rights Holder
      科学技術振興機構, 千葉大学
    • Industrial Property Number
      2004-146883
    • Filing Date
      2004-05-17
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Patent(Industrial Property Rights)] アジリジン類の製造方法2003

    • Inventor(s)
      石川 勉
    • Industrial Property Rights Holder
      科学技術振興機構
    • Industrial Property Number
      2003-057712
    • Filing Date
      2003-03-04
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Publications] W.Disadee, T.Watanabe, T.Ishikawa: "Polymer-Supported DMI as a Potential Heterogeneous Dehydrating Agent : Application to Esterification and Amidation"Synlett. 1号. 115-117 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] 石川 勉, 磯部 敏男: "グアニジン型キラル補助剤"有機合成化学協会誌. 61巻1号. 60-68 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Haga, T.Ishikawa: "Mechanistic Approaches to Asymmetric Cycle Synthesis of Aziridines from Guanidinium Ylides and Aryl Aldehydes"J.Am.Chem.Soc.. (発表予定).

    • Related Report
      2003 Annual Research Report
  • [Publications] Y.Furuta, T.Kumamoto, T.Ishikawa: "Direct Formation of Aziridines from Epoxides"Tetrahedron Lett.. (発表予定).

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Ishikawa, T.Isobe: "Modified Guanidines as Chiral Auxiliaries"Chemistry-A European Journal. 8巻・3号. 552-557 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] 石川 勉: "ニューグアニジンケミストリー"ファルマシア. 38巻・6号. 505-507 (2002)

    • Related Report
      2002 Annual Research Report

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Published: 2002-04-01   Modified: 2016-04-21  

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