Synthesis of conjugated enynes by magnesiumcarbenoid 1,2-CC insertion as the key reaction

DOI
  • Ishida Naoyuki
    Graduate School of Chemical Sciences and Technology, Tokyo University of Science
  • Saitoh Hideki
    Graduate School of Chemical Sciences and Technology, Tokyo University of Science
  • Satoh Tsuyoshi
    Graduate School of Chemical Sciences and Technology, Tokyo University of Science

Bibliographic Information

Other Title
  • マグネシウムカルベノイドの転位反応を鍵反応とする共役エンイン化合物の新規合成法

Description

The reaction of 1-chlorovinyl p-tolyl sulfoxides, which were derived from ketones and chloromethyl p-tolyl sulfoxide, with lithium acetylides gave adducts in moderate to good yields. Treatment of the adducts with Grignard reagents resulted in the formation of magnesium carbenoids by the sulfoxide-magnesium exchange reaction. 1,2-Carbon–carbon insertion (1,2-CC insertion) reaction of the generated magnesium carbenoids took place to afford conjugated enynes in good to high yields. Starting there reactions from unsymmetrical ketones, the 1,2-CC insertion was proved to be stereospecific. Furthermores the reaction of 1-chlorovinyl p-tolyl sulfoxides, which were derived from aldehydes, with lithium acetylides gave conjugated enynes via 1,2-Carbon–hydrogen insertion (1,2-CH insertion) reaction of the generated lithium carbenoids inermediates. This procedure provides a good method for the synthesis of multi-substituted conjugated enynes.

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Keywords

Details 詳細情報について

  • CRID
    1390282680612140928
  • NII Article ID
    130006997906
  • DOI
    10.14895/hannou.36.0.12.0
  • Text Lang
    ja
  • Data Source
    • JaLC
    • CiNii Articles
  • Abstract License Flag
    Disallowed

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