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2007 Fiscal Year Final Research Report Summary

Elucidafion of Origin of"Syn-Effect" and Application to Organic Synthesis

Research Project

Project/Area Number 18550030
Research Category

Grant-in-Aid for Scientific Research (C)

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

Principal Investigator

UKAJI Yutaka  Kanazawa University, Graduate School of Natural Science and Technology, Professor (80193853)

Project Period (FY) 2006 – 2007
Keywordssvn-effect / δ→π* interaction / olefin / 1.4-elimination / dienvl sulfone / steric hindrance / [1,2]-Wittig rearrangement / dienyl alcohol
Research Abstract

Stereochemistry of the 1,4-eliminative ring opening of [3-substituted (E) -1-propenyl]oxiranes to the corresponding 2,4-dienyl alcohols by LDA was investigated. The Z/E ratios of the resulting 2, 4-dienyl alcohols varied with the substituents at 3-position of the propenyl group. This phenomenon was discussed based on the concept of a "syn-effect," which is most primarily rationalized by a σ→π* interaction.
Stereochemistry of nucleophilic addition of amines to (E) -1-tosyl-l,3-butadiene was investigated. The Z/E ratios of the resulting allylic sulfones varied with amines, solvents, temperature, and concentration. When diethylamine was reacted in low concentration at higher temperature, the corresponding sterically unfavorable (Z) -4-amino-2-butenyl sulfone was preferentially obtained. Stereochemistry of nucleophilic addition of amines to ethyl (E)-2,4-pentadienoate, which possesses an ester group as a conjugated electron-withdrawing group instead of p-toluenesulfonyl(Ts) group, was also investigated to realize similar high (Z)-selectivity. The predominant formation of (Z)-isomers in both cases was rationalized by a "syn-effect," which might be mainly due to n/σ→π* interaction and/or 6r-electron homoaromaticity.
In the case of δ-benzyloxy substituted vinyloxiranes, [1,2]-Wittig rearrangement proceeded following the initial 1,4-eliminative ring opening to give a (E,Z) -2,4-dienyl 1,6-diols in a completely stereoselective manner. The sequential 1,4-eliminative ring opening-[1,2]-Wittig rearrangement also proceeded using α, α-dimethyl allylic sulfones to give the corresponding (Z)-dienyl alcohols.

  • Research Products

    (10 results)

All 2008 2007 2006 Other

All Journal Article (6 results) (of which Peer Reviewed: 3 results) Presentation (4 results)

  • [Journal Article] Syn Effect" in Nucleophilic Addition of Amines to(E)-1-Tosyl-1, 3-butadiene and Ethyl(E)-2,4-Pentadienoate2008

    • Author(s)
      M. Yamazaki, S. K. Guha, Y. Ukaji, and K. Inomata
    • Journal Title

      Bull. Chem. Soc. Jpn. 81(掲載確定)

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Asymmetric Addition of Phenylzinc Reagents to C-Alkyny1 Nitrones. Enantiomeric Enhance-ment by a Product-like Additive2008

    • Author(s)
      W. Wei, Y. Hamamoto, Y. Ukaji, and K. Inomata
    • Journal Title

      Tetrahedron Asymmetry 19

      Pages: 476-481

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] Asymmetric 1, 3-Dipolar Cycloaddition Reaction of Azomethine Imines to Ally1 Alcohol2008

    • Author(s)
      T. Kato, S.Fujinami, Y. Ukaji, and K. Inomad
    • Journal Title

      Chem. Lett 37

      Pages: 342-343

    • Description
      「研究成果報告書概要(和文)」より
    • Peer Reviewed
  • [Journal Article] "Syn Effect" in Nucleophilic Addition of Amines to (E)-l-Tosyl-1,3-butadiene and Ethyl(E)-2,4-Pentadienoate2008

    • Author(s)
      M. Yamazaki, S. K. Guha, Y. Ukaji, K. Inomata
    • Journal Title

      Bull. Chem. Soc (in press)

      Pages: 81

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Asymmetric Addition of Phenylzinc Reagents to C-Alkynyl Nitrones. Enantiomeric Enhancement by a Product-like Additive2008

    • Author(s)
      W. Wei, Y. Hamamoto, Y. Ukaji, K. Inomata
    • Journal Title

      Tetrahedron Asynunetry 19, 4

      Pages: 476-481

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Syn-Effect in Nucleophilic Addition of Amines to 1,3-Dienylsulfone2006

    • Author(s)
      M. Yamazaki, S. K. Guha, Y. Ukaji K. Inomata
    • Journal Title

      Chem. Lett 35, 5

      Pages: 514-515

    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] 1,4-脱離型反応における「シン効果」と連続する[1,2]-Wittig転位2008

    • Author(s)
      石丸勇雄, 竹田尚弘, 宇梶 裕, 猪股勝彦
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      東京
    • Year and Date
      2008-03-28
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] 1,4-脱離型反応における「シン効果」と連続する[1,2]-Wittig転位2007

    • Author(s)
      石丸勇雄, 竹田尚弘, 宇梶 裕, 猪股勝彦
    • Organizer
      有機合成化学北陸セミナー
    • Place of Presentation
      金沢
    • Year and Date
      2007-10-12
    • Description
      「研究成果報告書概要(和文)」より
  • [Presentation] Syn-Effect in 1,4-Eliminative Reaction and Subsequent[1,2]-Wittig Rearrangement

    • Author(s)
      I. Ishimaru, N. Takeda, Y. Ukaji, K. Inomata
    • Organizer
      the 88th annual meeting of the Chemical Society of Japan
    • Description
      「研究成果報告書概要(欧文)」より
  • [Presentation] Syn-Effect in 1,4-Eliminative Reaction and Subsequent[l,2]-Wittig Rearrangement

    • Author(s)
      I. Ishimaru, N. Takeda, Y. Ukaji, K. Inomata
    • Organizer
      Organic Synthesis Seminar in Hokuriku
    • Description
      「研究成果報告書概要(欧文)」より

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Published: 2010-02-04  

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