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Diastereoselective Construction of Contiguous Chilal Centers by the Aldol Reaction of Acylsilane Silyl Enol Ethers.

Research Project

Project/Area Number 03650694
Research Category

Grant-in-Aid for General Scientific Research (C)

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionKANAZAWA UNIVERSITY

Principal Investigator

NAKAJIMA Tadashi  KANAZAWA University, Faculty of Engineering, Department of Chemistry and Chemical Engineering. Professor., 工学部, 教授 (70019735)

Co-Investigator(Kenkyū-buntansha) SEGI Masahito  KANAZAWA University, Faculty of Engineering, Department of Chemistry and Chemica, 工学部, 講師 (90135046)
Project Period (FY) 1991 – 1992
Project Status Completed (Fiscal Year 1992)
Budget Amount *help
¥1,900,000 (Direct Cost: ¥1,900,000)
Fiscal Year 1992: ¥400,000 (Direct Cost: ¥400,000)
Fiscal Year 1991: ¥1,500,000 (Direct Cost: ¥1,500,000)
KeywordsSilyl enol ether / Acylsilane / Aldol Reaction / Acetal / Stereoselective Reaction / Protiodesilylation / シリルエノ-ルエ-テル / アセタ-ル / アルド-ル反応 / 高立体選択的反応 / 脱シリルプロトン化
Research Abstract

There has been considerable interest in recent years in the stereoselective formation of multiple chiral centers using aldol reaction between prochiral enolates and aldehydes. We disclosed here an convenient method of diastereoselective construction of the three or four contiguous chiral centers using the Lewis acid mediated reaction of acylsilane silyl enol ethers (I) with acetals and the subsequent nucleophilic addition to the carbonyl group of the resulting acylsilanes (II).
Treatment of E-or Z-acylsilane silyl enol ethers (I) derived from acylsilanes having enolizable methylene proton with a mixture of aldehyde dimethylacetals and TiCl_4 in dichloromethane gave the corresponding 2,3-anti-3-methoxy-1-silyl-1-alkanones (II) in high diastereo excess,independent of the double bond stereochemistry of I used. The similar reaction of E-I with d,1-phenylpropionealdehyde afforded 2,3-syn-3,4-syn-3-methoxy-1-silyl-1-butanal (V) in high stereoselectivity.
The resulting acylsilane 2,3-anti-II and 2,3-syn-3,4-syn-V were subjected to the nucleophilic reaction with alkyl or phenyllithium to yield the corresponding 3-methoxy-1-silyl-1-alkanols with three and four contiguous asymmetric centers (III and VI, respectively) stereoselectively. The protiodesilylation of III and VI with F^- reagent to afford the corresponding 1,2-anti-al- kanols with three and four contiguous asymmetric centers, IV and VII in 95-99% diastereo excess.

Report

(3 results)
  • 1992 Annual Research Report   Final Research Report Summary
  • 1991 Annual Research Report
  • Research Products

    (11 results)

All Other

All Publications (11 results)

  • [Publications] Tadashi Nakajima: "Reaction of Acylsilanes with Meta-stable Phosphonium ylides and Phosphonium diylides." Bull.Chem.Soc.Jpn.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Tadashi Nakajima: "Diastereoselective Construction of Three Contiguous Chiral Centers using Acylsilane Silyl Enol Ethers." Bull.Chem.Soc.Jpn.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Tadashi Nakajima: "Diastereoselective Construction of Four Contiguous Chiral Centers by the Reaction of Acylsilane Silyl Enol Ethers with α-Chiral Aldehydeacetal." Chem.Lett.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Tadashi Nakajima: "Reaction of Acylsilanes with Meta-stable Phosphonium ylides and Phosphonium diylides." Bull. Chem. Soc. Jpn.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Tadashi Nakajima: "Diastereoselective Construction of Three Contiguous Chiral Centers using Acylsilane Silyl Enol Ethers." Bull. Chem. Soc. Jpn.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Tadashi Nakajima: "Diastereoselective Construction of Four Contiguous Chiral Centers by the Reaction of Acylsilane Silyl Enol Ethers with a-Chiral Aldehydeacetal." Chem. Lett.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1992 Final Research Report Summary
  • [Publications] Tadashi Nakajima: "Reaction of Acylsilanes with Meta-stable Phosphonium ylides and Phosphonium diylides." Bull.Chem.Soc.Jpn.

    • Related Report
      1992 Annual Research Report
  • [Publications] Tadashi Nakajima: "Diastereoselective Construction of Three Contiguous Chiral Centers using Acylsilane Silyl Enol Ethers." Bull.Chem.Soc.Jpn.

    • Related Report
      1992 Annual Research Report
  • [Publications] Tadashi Nakajima: "Diastereoselective Construction of Four Contiguous Chiral Centers by the Reaction of Acylsilane Silyl Enol Ethers with α-Chiral Aldehydeacetal." Chem.Lett.

    • Related Report
      1992 Annual Research Report
  • [Publications] Tadashi Nakajima: "Diastereoselective Construction of Three Contiguous Chiral Centers using Acylsilane Silyl Enol Ethers" Bull.Chem.Soc.Jpn.,.

    • Related Report
      1991 Annual Research Report
  • [Publications] Tadashi Nakajima: "Enantioselective Aldol Condensation of Chiral Acylsilane Silyl Enol Ether with Acetal" Chem.Letters.

    • Related Report
      1991 Annual Research Report

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Published: 1991-04-01   Modified: 2016-04-21  

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