Nickel-Catalyzed Dimerization of [5]Cumulenes (Hexapentaenes)

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Abstract

Tetraaryl[5]cumulenes react with low-valent nickel complexes at the second double bond to produce novel [4]radialene derivatives that are head-to-head dimers of [5]cumulenes. The head-to-head dimers are also synthesized by a stepwise route. On the other hand, the nickel-catalyzed dimerization of [5]cumulenes with bulky substituents produces other types of extended [4]radialenes and [5]radialenones depending on the bulkiness of the terminal alkyl substituents. Thus, tetrakis-<I>t</I>-butyl[5]cumulene and 1,4-bis(2,2,6,6-tetramethylcyclohexylidene)[3]cumulene react at the central double bond to give the corresponding [4]radialene and [5]radialenone, whereas 1,4-bis(2,2,5,5-tetramethylcyclopentylidene)[3]cumulene and its benzo-annelated derivative react at the second double bond in a head-to-tail manner to afford the corresponding extended [4]radialenes. Tetrakis-<I>t</I>-butyl[5]radialenone was converted into [5]radialene by using a methylation–dehydration procedure. The extended [4]- and [5]radialenes and [5]radialenones have been fully characterized by spectroscopic analyses, X-ray crystallography, and/or independent chemical synthesis. The properties of these novel exocyclic π-electron systems have been investigated in detail. The aryl-substituted [4]radialenes exhibit facile bond rotation with low energy barriers. The [5]radialene and [5]radialenone form the corresponding cations easily by the addition of an acidic proton. The selectivity of the nickel-catalyzed dimerization of [5]cumulenes is discussed on the basis of theoretical calculations.

Journal

  • Bulletin of the Chemical Society of Japan

    Bulletin of the Chemical Society of Japan 78(12), 2188-2208, 2005-12-15

    The Chemical Society of Japan

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Codes

  • NII Article ID (NAID)
    10017074742
  • NII NACSIS-CAT ID (NCID)
    AA00580132
  • Text Lang
    ENG
  • Article Type
    ART
  • ISSN
    00092673
  • NDL Article ID
    7741492
  • NDL Source Classification
    ZP1(科学技術--化学・化学工業)
  • NDL Call No.
    Z53-B35
  • Data Source
    CJP  NDL  J-STAGE 
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