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Development of versatile synthetic route for 1,2-diamines as excellent chiral auxiliary.

Research Project

Project/Area Number 08672431
Research Category

Grant-in-Aid for Scientific Research (C)

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

Principal Investigator

ISHIZUKA Tadao  Kumamoto University, Pharmaceutical Sciences ; Associate Professor., 薬学部, 助教授 (60176203)

Project Period (FY) 1996 – 1997
Project Status Completed (Fiscal Year 1997)
Budget Amount *help
¥1,900,000 (Direct Cost: ¥1,900,000)
Fiscal Year 1997: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 1996: ¥1,300,000 (Direct Cost: ¥1,300,000)
Keywords2-Imidazolone / 2-Imidazolidinone / 1,2-Diamine / Optical resolution / Chiral auxiliary / Chiral synthesis / 1,2-ジアミン
Research Abstract

1.Versatile Syunthetic Route for 1,2-Diamines from 2-Imidazolone.
2-Imidazolone was proved to be a excellent building block for the synthesis of 1,2-diamines. Wide variety of trans-4,5-disubstituted 2-imidazolidinones could by synthesized by an addition reaction of Br_2 to the olefinic moiety of the 2-imidazolone and subsequent substitution reactions. Hydorlytic conversion to 1,2-diamines also succeeded.
2.Conformationally Fixed 2-Imidazolidinones as Chiral Auxiliaries.
Both enantiomers of sterically congested 2-imidazolidinones, which served as efficient chiral auxiliaries, were synthesized by [4+2] cycloaddition of cyclic dienes with 2-imidazolone. The utilities of these auxiliaries in asymmetric synthetic reactions such as alkylations, the Diels-Alder reactions and aldol ractions were revealed.
3.Conversion of 1,2-Diamines to 2-Imidazolines.
2-Imidazolines were synthesized by dehydration reactions of the amide derivatives of the 1,2-diamines by phosphorus oxychloride. Further applications as chiral ligands are now in progress.

Report

(3 results)
  • 1997 Annual Research Report   Final Research Report Summary
  • 1996 Annual Research Report
  • Research Products

    (27 results)

All Other

All Publications (27 results)

  • [Publications] Tadao Ishizuka: "Highly Efficient Chiral Auxiliaries : Sterically Constrained 2-Oxazolidinones and Derived Amino Alcohols" Reviews on Heteroatom Chemistry. 15. 227-241 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Noriaki Hashimoto: "Reversal of Stereoselection in Diastereodivergence of Meso-Dicarboxylic Anhydrides." Tetrahedron Lett.37. 9237-9240 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Takahumi Kouyama: "Facile Synthesis of (+) -and (-) -Geissman-Weiss Lactones" Heterocycles. 44. 479-486 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Hirofumi Matsunaga: "Chiral Electrophilic “Glycical" Equivalents. New Synthons for Optically Active α-Amino Acids and 4-substituted 2-Oxazolidinones" Tetrahedron. 53. 1275-1294 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Taiju Nakamura: "Sterically Constrained Tricyclic 2-Oxazolidinone as Excellent Chiral Auxiliary" Tetrahedron Lett.38. 559-562 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] 石塚 忠雄: "2-アミノアルコール系人工不斉源の開発研究" 薬学雑誌. 117. 339-352 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Noriaki Hashimoto: "The Highly Enantioselective Borane Reduction of Ketones Catalyzed by Chiral Oxazaboloridine Derived from Sterically Constrained Amino Alcohols." Heterocycles. 46. 189-192 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Takehisa Kunieda: "Synthetic Veresatality of 2-Oxazolone Heterocycle for Stereo-controlled Construction of 2-Amino Alcohol." J.Synth.Org.Chem.,Jan. 55. 1018-1028 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Tadao Ishizuka: "Highly Efficient Chiral Auxiliaries : Sterically Constrained 2-Oxazolidinones and Derived Amino alcohols" Reviews on Heteroatom Chemistry. 15. 227-241 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Noriaki Hashimoto: "Reversal of Stereoselection in Diastereo-divergence of Meso-Dicarboxylic Anhydrides." Tetrahedron Lett.37. 9237-9240 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Kouyama Takahumi: "Facile Synthesis of (+)- and (-)-Geissman-Waiss Lactones" Heterocycles.44. 479-486 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Hirohumi Matsunaga: "Chiral Electrophilic "Glycinal" Equivalents. New Synthons for Optically Active alpha-Amino Acids and 4-substituted 2-Oxazolidinones." Tetrahedron. 53. 1275-1294 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Taijyu Nakamura: "Sterically Constrained Tricyclic 2-Oxazolidinone as Excellent Chiral Auxiliary" Tetrahedron Lett.38. 559-562 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Tadao Ishizuka: "Synthetic 2-Amino Aocohol Derivatives as Chiral Auxiliaries" Yakugaku zasshi. 117. 339-352 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Noriaki Hashimoto: "The Highly Enantioselective Borane Reduction of Ketones Catalyzed by Chiral Oxazaboloridine Derived from Sterically Constrained Amino Aocohols" Heterocycles. 46. 189-192 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Takehisa Kunieda: "Synthetic Versatility of 2-Oxazolone Heterocycle for Stereo-controlled Construction of 2-Amino Alcohols." J.Synth.Org.Chem., Jpn.55. 1018-1028 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1997 Final Research Report Summary
  • [Publications] Takahumi Kouyama: "Facile Synthesis of (+)-and (-)-Geissman-Weiss Lactones" Heterocycles. 44. 479-486 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Hirofumi Matsunaga: "Chiral Electrophilic "Glycinal"Equivalents.New Synthons for Optically Active α-amino Acids and 4-substituted 2-Oxazolidinones" Tetrahedron. 53. 1275-1294 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Taiju Nakamura: "Sterically Constrained Tricyclic 2-Oxazolidinone as Excellent Chiral Auxiliary" Tetrahedron Lett.38. 559-562 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] 石塚忠男: "2-アミノアルコール系人工不斉源の開発研究" 薬学雑誌. 117. 339-352 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Noriaki Hashimoto: "The Highly Enantioselective Borane Reduction of Ketones Catalyzed by Chiral Oxazaboloridine Derived from Sterically Constrained Amino Alcohols." Heterocycles. 46. 189-192 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Takehisa Kunieda: "Synthetic Veresatality of 2-Oxazolone Heterocycle for Stereo-contraolled Construction of 2-Amino Alcohols." J.Synth.Org.Chem.,Jpn. 55. 1018-1028 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Tadao Ishizuka: "Highly Efficient Chiral Auxiliaries : Sterically Constrained 2-Oxazolidinones and Derived Amino Alcohols" Reviews on Heteroatom Chemistry. 15. 227-241 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Noriaki Hashimoto: "Reversal of Stereoselection in Diastereodivergence of Meso-Dicarboxylic Anhydrides." Tetrahedron Lett.37. 9237-9240 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] Takahumi Kouyama: "Facile Synthesis of (+) -and (-) -Geissman-Weiss Lactones" Heterocycles. 44. 479-486 (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] Hirofumi Matsunaga: "Chiral Electrophilic "Glycinal" Equivalents. New Synthons for Optically Active α-Amino Acids and 4-substituted 2-Oxazolidinones" Tetrahedron. 53. 1275-1294 (1997)

    • Related Report
      1996 Annual Research Report
  • [Publications] Taiju Nakamura: "Sterically Constrained Tricyclic 2-Oxazolidinone as Excellent Chiral Auxiliary" Tetrahedron Lett.38. 559-562 (1997)

    • Related Report
      1996 Annual Research Report

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Published: 1996-04-01   Modified: 2016-04-21  

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