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The First Spiro Isoxazoline Ligands

Research Project

Project/Area Number 11440190
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionOsaka University

Principal Investigator

SASAI Hiroaki  The Institute of Scientific and Industrial Research, Professor, 産業科学研究所, 教授 (90205831)

Co-Investigator(Kenkyū-buntansha) TAKIZAWA Shinobu  The Institute of Scientific and Industrial Research, Research Associate, 産業科学研究所, 助手 (50324851)
荒井 孝義  大阪大学, 産業科学研究所, 助手 (80272483)
Project Period (FY) 1999 – 2001
Project Status Completed (Fiscal Year 2001)
Budget Amount *help
¥14,400,000 (Direct Cost: ¥14,400,000)
Fiscal Year 2001: ¥2,900,000 (Direct Cost: ¥2,900,000)
Fiscal Year 2000: ¥4,200,000 (Direct Cost: ¥4,200,000)
Fiscal Year 1999: ¥7,300,000 (Direct Cost: ¥7,300,000)
KeywordsSpiro / Isoxazoline / Asymmetric / Catalyst / Cyclization / Tandem Reaction / Aminocarbonylation / Palladium / イソオキサゾリン / オキシパラデーション / 配位子 / Wacker反応 / タンデム / スピロ化合物 / SPRIX / マイケル反応 / Wacker触媒 / 光学活性配位子 / パラジウム錯体
Research Abstract

We had great interest in the chelating ability of isoxazolines on the basis of ab initio calculations. In this project, we have designed, and synthesized the first chiral bis(isoxazoline) ligands (SPRIXs) containing rigid spiro skeleton. The ligands showed great affinity towards Pd(II) salts and the resulting chiral Pd(II)-spiro bis(isoxazoline) catalysts promoted the catalytic asymmetric Wacker-type cyclization of alkenyl alcohols. Furthermore, a new catalytic asymmetric tandem cyclization of dialkenylalcohol took place, affording a unique bicyclic ether in one step with up to 95% ee. New type of bis(isoxazoline) ligands, 2,2'-bis(isoxazolinyl)propane and (R)-2,2'-bis(isoxazolinyl)-1,1'-binaphthyl have been prepared and strong ligand-acceleration effects were demonstrated in Pd(II)-catalyzed Wacker-type cyclization of alkenyl alcohol. The lack of acceleration effects with oxazoline ligands clearly shows the crucial role of isoxazoline moiety on the Wacker-type cyclization of alkenyl alcohols. In the presence of carbon monoxide the Pd(II)-spiro bis(isoxazoline) catalyst also promoted the asymmetric carbonylation of alkenyl amines or alcohols to give pyrrolidines or lactones with moderate enantioselectivities.

Report

(4 results)
  • 2001 Annual Research Report   Final Research Report Summary
  • 2000 Annual Research Report
  • 1999 Annual Research Report
  • Research Products

    (19 results)

All Other

All Publications (19 results)

  • [Publications] 笹井 宏明: "Design and Synthesis of the First Spiro Bis(isoxazoline) Derivatives as Asymmetric Ligands"Organic Letters. 1. 1795-1797 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 笹井 宏明: "A New Asymmetric Wacker-type Cyclization and Tandem Cyclization Promoted by Pd(II)-Spiro Bis(isoxazoline) Catalyst"Journal of the American Chemical Society. 123. 2907-2908 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 笹井 宏明: "Synthesis of New Chiral Bis(isoxazoline) Ligands Containing Spiro[5.5]undecane Skeltone"Chirality. 15. 101-104 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 笹井 宏明: "The First Enantioselective Intramolecular Amino-carbonylarion of Alkynes Promoted by Pd(II)-Spiro Bis(isoxazoline) Catalyst"Tetrahedron Letters. 44. 711-714 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 笹井 宏明: "Synthesis and Character of New Bis(isoxazoline) Ligands"Heterocycles. 59. 587-593 (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 笹井 宏明: "スピロビスイソオキサゾリン配位子(SPRIXs)を用いる触媒的不斉合成反応の開発"有機合成化学協会誌. 59. 466-467 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 笹井 宏明: "My Favorite Organic Synthesis"The Society of Synthetic Organic Chemistry. 176-177 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] 笹井 宏明: "Latest Frontiers of Organic Synthesis"Research Signpost. 49-64 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Arai, M. A., Arai, T., Sasai, H.: "Design and Synthesis of the First Spiro Bis(isoxazoline) Derivatives as Asymmetric Ligands"Organic Letters. 1. 1795-1797 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Arai, M. A., Kuraishi, M., Arai, T., Sasai, H.: "A New Asymmetric Wacker-type Cyclization and Tandem Cyclization Promoted by Pd(II)-Spiro Bis(isoxazoline) Catalyst"Journal of the American Chemical Society. 123. 2907-2908 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Arai, M. A., Kuraishi, M., Arai, T, Sasai, H.: "Synthesis of New Chiral Bis(isoxazoline) Ligands Containing Spiro[5.5]undecane Skeltone"Chirality. 15. 101-104 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Shinohara, T., Arai, M. A., Wakita, K., Arai, T., Sasai, H.: "The First Enantioselective Intramolecular Amino-carbonylation of Alkynes Promoted by Pd(II)-Spiro Bis(isoxazoline) Catalyst"Tetrahedron Letters. 44. 711-714 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Shinohara, T., Wakita, K., Arai, M. A., Arai, T., Sasai, H.: "Synthesis and Character of New Bis(isoxazoline) Ligands"Heterocyctes. 59. 587-593 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Arai, M. A., Arai, T., Sasai, H.: "Development of the First Spiro Bis(isoxazoline) Ligands (SPRIXs)"Latest Frontiers of Organic Synthesis, Research Signpost, Y. Kobayashi (Editor). 49-64 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Sasai, H., Arai, M. A.: "Study on Chiral Spiro Bis(isoxazoline) Ligand (SPRIX)"My Favorite Organic Synthesis, The Soeiety of Synthetic Organic Chemistry, K. Tatsuta (Editor). 176-177 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2001 Final Research Report Summary
  • [Publications] Arai, Midori A.: "A New Asymmetric Wacker-Type Cyclization and Tandem Cyclization Promoted by Pd(II)-Spiro Bis(isoxazoline) Catalyst"J. Am. Chem. Soc.. 123(12). 2907-2908 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] 笹井 宏明: "スピロビスイソオキサゾリン配位子(SPRIXs)を用いる触媒的不斉合成法の開発"有機合成化学協会誌. 59(5). 466-467 (2001)

    • Related Report
      2001 Annual Research Report
  • [Publications] M.A.Arai: "A New Asymmetric Wacker-Type Cyclization and Tandem Cyclization Promoted by Pd (II)-Spiro Bis (isoxazoline) Catalyst"J.Am.Chem.Soc.. 123(印刷中). (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] Midori A. Arai: "Design and Synthesis of the First Spiro Bis(isoxazoline) Derivatives as Asymmetric Ligands"Organic Letters. 1・11. 1795-1797 (1999)

    • Related Report
      1999 Annual Research Report

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Published: 1999-04-01   Modified: 2016-04-21  

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