CaCl_3-Promoted Addition Reactions of Carbon Nuclecophiles to Alkyne

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Abstract

GaCl<SUB>3</SUB> promotes addition reactions of carbon nucleophiles to a C-C triple bond. Interaction of alkyne with GaC1<SUB>3</SUB> generates a highly reactive electrophile, which aromatic hydrocarbon attacks to give an alkenylated arene. Silylethyne reacts predominantly at the <I>p</I>-position of toluene, while disilylated 1, 3-butadiyne exhibits <I>o</I>-selectivity. The behavior of a silylated 1, 2-propadiene is intermediate between that of the silylethyne and the disilylated 1, 3-butadiyne. In the presence of GaCl<SUB>3</SUB>, electrophilic trimerization of silylethyne takes place to give a conjugated hexatriene. In this reaction, silylethyne attacks the GaCl<SUB>3</SUB>-activated C-C triple bond. Carbometalation is another interesting addition reaction of an organogallium compound to alkyne. Alkynyldichlorogallium dimerizes in hydrocarbon solvents to give 1, 1-dimetallo-l-buten-3-yne. In the presence of GaCl<SUB>3</SUB>, silyl enol ether is ethenylated at the α-carbon atom with trimethylsilylethyne. Treatment of lithium phenoxide with silylethyne in the presence of GaCl<SUB>3</SUB> gives <I>o</I>- (β-silylethenyl) phenol. These reactions involve carbogallation of alkynylgallium, gallium enolate, or gallium phenoxide.

Journal

  • Journal of Synthetic Organic Chemistry, Japan

    Journal of Synthetic Organic Chemistry, Japan 58(11), 1030-1036, 2000-11-01

    The Society of Synthetic Organic Chemistry, Japan

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Codes

  • NII Article ID (NAID)
    10008821934
  • NII NACSIS-CAT ID (NCID)
    AN0024521X
  • Text Lang
    ENG
  • Article Type
    REV
  • ISSN
    00379980
  • NDL Article ID
    5549650
  • NDL Source Classification
    ZP11(科学技術--化学・化学工業--有機化学・有機化学工業)
  • NDL Call No.
    Z17-256
  • Data Source
    CJP  NDL  J-STAGE 
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