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Creation of Novel Axially-Chiral Compounds : Developments toward Asymmetric Synthesis

Research Project

Project/Area Number 06453189
Research Category

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

Allocation TypeSingle-year Grants
Research Field Chemical pharmacy
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

FUJI Kaoru  Kyoto University, Institute for Chemical Research Professor, 化学研究所, 教授 (20027056)

Co-Investigator(Kenkyū-buntansha) KAWABATA Takeo  Kyoto University, Institute for Chemical Research Instructor, 化学研究所, 助手 (50214680)
TANAKA Kiyoshi  Kyoto University, Institute for Chemical Research Associate Professor, 化学研究所, 助教授 (50093266)
Project Period (FY) 1994 – 1995
Project Status Completed (Fiscal Year 1995)
Budget Amount *help
¥7,400,000 (Direct Cost: ¥7,400,000)
Fiscal Year 1995: ¥1,800,000 (Direct Cost: ¥1,800,000)
Fiscal Year 1994: ¥5,600,000 (Direct Cost: ¥5,600,000)
KeywordsAxial Chirality / Asymmetric Protonation / Asymmetric Olefination / 1,1'-Binaphthalene-2,2'-diol / 1,1'-Binaphthalene-8,8'-diol / Wittig Reaction / 軸不斉化合物 / 不斉合成 / Horner-Wadsworth-Emmons反応 / エノレート / α-ジケトン / σ-対称 / プロキラル
Research Abstract

This research project has dealt with asymmetric synthesis using axially chiral compounds which possess 1,1'-binaphthalene skeleton. Especially, asymmetric Wittig reaction and asymmetric protonation were examined. Since Wittig reaction creates sp^2 carbon, its application to asymmetric synthesis had rather been limited. We demonstrated asymmetrization of sigma-symmetrical meso-compounds through discrimination of enantiotopic carbonyls of alpha-diketones. Using chiral phosphonates having 1,1'-binaphthalene-2,2'-diol moiety as a chiral auxiliary, highly enantioselective Wittig-type reactions were achieved with rigid cyclic alpha-diketones. Intramolecular Asymmetric Witting-type reactions were also performed to afford polycyclic ketones in moderate to high enantioselectivity.
Since protonation is one of the most simple operations out of chemical transformations, asymmetric protonation of enolates should have wide variety of applications to production of optically active carbonyl compounds. We have investigated asymmetric protonation using chiral proton sources having 1,1'-binaphthalene-8,8'-diol moiety. Enantioselectivity of the protonation depended strongly on the countercation of the enolates. While the lithium enolate of an alpha-tetralone derivative gave the products of only 9% ee, the corresponding magnesium enolare afforded the product of 94% ee.

Report

(3 results)
  • 1995 Annual Research Report   Final Research Report Summary
  • 1994 Annual Research Report
  • Research Products

    (14 results)

All Other

All Publications (14 results)

  • [Publications] Kaoru Fuji: "Diastereoselectivity in Addition of Methylmagnesium Halide to Benzoylformate of Chiral 1,1′-Binaphthalene-2,2′-diol" Chem. Pharm. Bull.42. 957-959 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Kaoru Fuji: "Enantioselective Protonation of Enolates: Novel Chiral Proton Sources and Remarkable Effects of the Countercation" J. Org. Chem.,. 60. 1914-1915 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Kiyoshi Tanaka: "Asymmetric Michael Addition Reactions of Chiral Prop-2-enyl-and But-2-enylphosphonate Anions with Cyclic Enones" J. Org. Chem.,. 60. 8036-8043 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Fujie Tanaka: "1,1′-Binaphthalene-2,2′-diol as a Chiral Auxiliary . Diastereoselective Alkylation of Binaphthyl Esters, Complex-Induced Proximity Effects in Enolate Formation, and One-Step Synthesis of an Optically Active β-Substituted Ketone" J. Am. Chem. Soc.,. 117. 12159-12171 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Kaoru Fuji: "Diastereoselectivity in Addition of Methylmagnesium Halide to Benzoylformate of Chiral 1,1'-Binaphthalene-2,2'-diol" Chem.Pharm.Bull.42. 957-959 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Kaoru Fuji: "Enantioselective Protonation of Enolates : Novel Chiral Proton Sources and Remarkable Effects of the Countercation" J.Org.Chem.60. 1914-1915 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Kiyoshi Tanaka: "Asymmetric Michael Addition Reactions of Chiral Prop-2-enyl-and But-2-enylphosphonate Anions with Cyclic Enones" J.Org.Chem.60. 8036-8043 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Fujie Tanaka: "1,1'-Binaphthalene-2,2'-diol as a Chiral Auxiliary Diastereoselective Alkylation of Binaphthyl Esters, Complex-Induced Proximity Effects in Enolate Formation, and One-Step Synthesis of an Optically Active -Substituted Ketone" J.Am.Chem.Soc.117. 12159-12171 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Kaoru Fuji: "Enantioselective Protonation of Enolates:Novel Chiral Proton Source and Remarkable Effects of the Countercation" J. Org. Chem.60. 1914-1915 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Fujie Tanaka: "1,1′-Binaphthalene-2,2′-diol as a Chiral Auxiliary. Diastereoselective Alkylation of Binaphthy1 Esters, Complex-Induced Proximity Effects in Enolate Formation, and One-Step Synthesis of an Optically Active β-Substituted Ketone" J. Am. chem. Soc.117. 12159-12171 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Kiyoshi Tanaka: "Asynoretric Michael Addition Reactions of Chiral Prop-2-enyl- and But-2-enylophesphorate anions with Cyclic Enones" J. Org. Chem.60. 8036-8043 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Kaoru Fuji: "Diastereoselestivity in Addition of Methylmagnium Halide to Benzoyloformate of Chiral 1,1′-Binaphthalene-2-2′-diol" Chem. Pharm. Bull.42. 957-959 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Kaoru Fuji: "Diastereoselectivity in Addition of Methylmagnesium Halide to Benzoylformate of Chiral 1,1′-Binaphthalene-2,2′-diol" Chem.Pharm.Bull.42. 957-959 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Kaoru Fuji: "Enantioselective Protonation of Enolates:Novel Chiral Proton Sources and Remarkable Effects of the Counter Cation" J.Org.Chem.60. (1995)

    • Related Report
      1994 Annual Research Report

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Published: 1994-04-01   Modified: 2016-04-21  

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