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Chiral Triols of C3-symmetry : Synthesis and Application to Asymmetric Synthesis

Research Project

Project/Area Number 10640578
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field 物質変換
Research InstitutionKyoto Institute of Technology

Principal Investigator

ABIKO Atsushi  Associate professor, Kyoto Institute of Technology, Graduate School of Engineering, 工芸科学研究科, 助教授 (30184203)

Project Period (FY) 1998 – 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥3,200,000 (Direct Cost: ¥3,200,000)
Fiscal Year 2000: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 1999: ¥600,000 (Direct Cost: ¥600,000)
Fiscal Year 1998: ¥2,100,000 (Direct Cost: ¥2,100,000)
KeywordsDouble aldol reaction / Boron-mediated aldol reaction / Carboxylic ester / Asymmetric synthesis / Chiral triol of C3-symmetry / Chiral synthon / Doubly borylated enolate / Carbon-bound enolate / デンドリマー / グリニア反応
Research Abstract

We have devised a new asymmetric boron-mediated asymmetric double aldol reaction. Treatment of a chiral acetate ester with dicyclohexylboron triflate and triethylamine, followed by the reaction with aldehyde, afforded bis-aldols via a double aldol reaction with high selectivity. Chiral triols of C3-symmetry, which are potential precursors for the study of asymmetric catalysis and chiral recognition, have been synthesized from the double aldol products. Preliminary studies on the derivatization of the triols as well as the preparation of their metal complexes have been executed.
From the mechanistic study, the characteristic features of this novel reaction can be summarized as follows : (1) the double aldol reaction is specific to acetate esters, not to ketones or thioesters, (2) the stoichiometry of the boron triflate to acetate ester is 2 : 1 to achieve enolization of the acetate ester, (3) the second equivalent of the boron triflate is active for the double aldol reaction but inactive for enolization of an external thioester, (4) a β-boryloxyester, which is an intermediate of the single (conventional) aldol reaction, is not an intermediate of the double aldol reaction. We have clarified the mechanism of the double aldol reaction, and spectroscopically characterized an intermediate enolate species as a "doubly borylated enolate", which is the first carbon-bound boron enolate species.

Report

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

    (18 results)

All Other

All Publications (18 results)

  • [Publications] Abiko,A. et al: "The Boron-Mediated Double Aldol Reaction of Carboxylic Esters"J.Am.Chem.Soc.. 121巻・30号. 7168-7169 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] 安孫子淳: "ボロンアルドール反応の新展開"TCIメール. 107. 2 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Abiko,A.: "The first doubly borylated enolate as an intermediate of double aldol reaction"J.Am.Chem.Soc.. 123(印刷中). (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Abiko,A: "Dicyclohexylboron trifluoromethanesulfonate"Organic Synthesis. 78(印刷中). (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Abiko,A: "2-(N-Benzyl-N-mesitylenesulfonyl) amino-1-phenyl-1-propyl propionate"Organic Synthesis. 78(印刷中). (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Abiko,A: "Anti-selective boron-mediated asymmetric aldol reaction of carboxylic esters"Organic Synthesis. 78(印刷中). (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Abiko, A.: "The Boron-Mediated Double Aldol Reaction of Carboxylic Esters"J.Am.Chem.Soc.. 121, (30). 7168-9 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Abiko, A.: "New Aspects of Boron-mediated aldol reaction"TCI Mail. 107. 2 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Abiko, A.: "The first doubly borylated enolate as an intermediate of double aldol reaction"J.Am.Chem.Soc.. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Abiko, A.: "Dicyclohexylboron trifluoromethanesulfonate"In Organic Synthesis. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Abiko, A.: "2-(N-Benzyl-N-mesitylenesulfonyl) amino-1-phenyl-1-propyl propionate"In Organic Synthesis. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Abiko, A.: "Anti-selective boron-mediated asymmetric aldol reaction of carboxylic esters"In Organic Synthesis. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Abiko,A.: "The first doubly borylated enolate as an intermediate of double aldol reaction"J.Am.Chem.Soc.. 123(印刷中). (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] 安孫子淳: "ボロンアルドール反応の新展開"TCIメール. 107. 2 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Abiko,A: "Dicyclohexylboron trifluoromethanesulfonate"Organic Synthesis. 78(印刷中). (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] Abiko,A: "2-(N-Benzyl-N-mesitylenesulfonyl) amino-1-phenyl-1-propyl propionate"Organic Synthesis. 78(印刷中). (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] Abiko,A: "Anti-selective boron-mediated asymmetric aldol reaction of carboxylic esters"Organic Synthesis. 78(印刷中). (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] Abiko, A.et al.: "The Boron-Mediated Double Aldol Reaciton of Carboxylic Esters"J.Am.Chem.Soc.. 121巻・30号. 7168-7169 (1999)

    • Related Report
      1999 Annual Research Report

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Published: 1998-04-01   Modified: 2016-04-21  

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