"Syn-Effect" in the Desulfonylation Reaction of α,α-Dialkylated (E)-Allylic Sulfones "Syn-Effect" in the Desulfonylation Reaction of a, a-Dialkylated (E)-Allylic Sulfones

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Abstract

It was found that the desulfonylation reaction of α,α-dialkylated (E)-allylic sulfones with a base preferentially affords the sterically unfavorable (Z)-alkadienes. The relative degree of the "syn-effect", which is herein defined as an effect which stabilizes the syn-conformation, leading to (Z)-products, in the transition state against the steric hindrance, was revealed for various substituents at the δ-position of the (E)-allylic sulfones to be as follows: RO– >> CH3– > RS– > –CH2– > (CH3)2CH– >> (CH3)3C– > C6H5–. This finding is in accord with a previously found tendency in the conversion of (E)-vinylic sulfones to the corresponding allylic sulfones under basic conditions.

It was found that the desulfonylation reaction of <i>α</i>,<i>α</i>-dialkylated (<i>E</i>)-allylic sulfones with a base preferentially affords the sterically unfavorable (<i>Z</i>)-alkadienes. The relative degree of the “<i>syn-effect</i>”, which is herein defined as an effect which stabilizes the <i>syn</i>-conformation, leading to (<i>Z</i>)-products, in the transition state against the steric hindrance, was revealed for various substituents at the <i>δ</i>-position of the (<i>E</i>)-allylic sulfones to be as follows: RO– >> CH<sub>3</sub>– > RS– > –CH<sub>2</sub>– > (CH<sub>3</sub>)<sub>2</sub>CH– >> (CH<sub>3</sub>)<sub>3</sub>C– > C<sub>6</sub>H<sub>5</sub>–. This finding is in accord with a previously found tendency in the conversion of (<i>E</i>)-vinylic sulfones to the corresponding allylic sulfones under basic conditions.

Journal

  • Bulletin of the Chemical Society of Japan

    Bulletin of the Chemical Society of Japan 70(2), 381-396, 1997-02-15

    The Chemical Society of Japan

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Codes

  • NII Article ID (NAID)
    10008915913
  • NII NACSIS-CAT ID (NCID)
    AA00580132
  • Text Lang
    ENG
  • Article Type
    ART
  • ISSN
    00092673
  • NDL Article ID
    4153671
  • NDL Source Classification
    ZP1(科学技術--化学・化学工業)
  • NDL Call No.
    Z53-B35
  • Data Source
    CJP  NDL  IR  J-STAGE 
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