Download PDF
Synlett 2010(10): 1515-1518  
DOI: 10.1055/s-0029-1219944
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Selective Propargylation of Azo Compounds with Barium Reagents

Akira Yanagisawa*, Takanori Koide, Kazuhiro Yoshida
Department of Chemistry, Graduate School of Science, Chiba University, Inage, Chiba 263-8522, Japan
Fax: +81(43)2902789; e-Mail: ayanagi@faculty.chiba-u.jp;
Further Information

Publication History

Received 10 March 2010
Publication Date:
25 May 2010 (online)

    Permissions and Reprints All articles of this category

Abstract

A Barbier-type propargylation of azo compounds with γ-trialkylsilylated propargylic bromides has been achieved using reactive barium as a low-valent metal in THF. Corresponding propargylated hydrazines (α-adducts) were exclusively formed not only from azobenzenes (diaryldiazenes) but also from dialkyl azodicarboxylates. This method is also applicable to γ-alkylated or γ-phenylated propargylic bromides, providing the desired propargylated products only.

Key words

azo compounds - barium - hydrazine - propargylation - propargylic bromides

    References and Notes

  • For reactions of allylic barium reagents, see:
  • 1a Yanagisawa A. Habaue S. Yamamoto H. J. Am. Chem. Soc.  1991,  113:  8955 
    Google Scholar
  • 1b Yanagisawa A. Habaue S. Yasue K. Yamamoto H. J. Am. Chem. Soc.  1994,  116:  6130 
    Google Scholar
  • For reviews, see:
  • 1c Yanagisawa A. Yamamoto H. In Active Metals. Preparation, Characterization, Applications   Fürstner A. VCH; Weinheim: 1996.  p.61 
    Google Scholar
  • 1d Yanagisawa A. In Science of Synthesis   Vol. 7:  Yamamoto H. Thieme; Stuttgart: 2004.  p.695 
    Google Scholar
  • 1e Yanagisawa A. In Main Group Metals in Organic Synthesis   Vol. 1:  Yamamoto H. Oshima K. Wiley-VCH; Weinheim: 2004.  p.175 
    Google Scholar
  • For related strontium reagents, see:
  • 1f Miyoshi N. Kamiura K. Oka H. Kita A. Kuwata R. Ikehara D. Wada M. Bull. Chem. Soc. Jpn.  2004,  77:  341 
    Google Scholar
  • 1g Miyoshi N. Ikehara D. Kohno T. Matsui A. Wada M. Chem. Lett.  2005,  34:  760 
    Google Scholar
  • 1h Miyoshi N. In Science of Synthesis   Vol. 7:  Yamamoto H. Thieme; Stuttgart: 2004.  p.685 
    Google Scholar
  • 1i Miyoshi N. Ikehara D. Matsuo T. Kohno T. Matsui A. Wada M. J. Synth. Org. Chem. Jpn.  2006,  64:  845 
    Google Scholar
  • 2a Sell MS. Rieke RD. Synth. Commun.  1995,  25:  4107 
    Google Scholar
  • For reviews, see:
  • 2b Rieke RD. Sell MS. Klein WR. Chen T.-A. Brown JD. Hanson MV. In Active Metals. Preparation, Characterization, Applications   Fürstner A. VCH; Weinheim: 1996.  p.1 
    Google Scholar
  • 2c Rieke RD. Hanson MV. Tetrahedron  1997,  53:  1925 
    Google Scholar
  • 3 Yanagisawa A. Okitsu S. Arai T. Synlett  2005,  1679 
    Article in Thieme ConnectGoogle Scholar
  • 4 Yanagisawa A. Suzuki T. Koide T. Okitsu S. Arai T. Chem. Asian J.  2008,  3:  1793 
    CrossrefPubMedGoogle Scholar
  • 5a An DK. Hirakawa K. Okamoto S. Sato F. Tetrahedron Lett.  1999,  40:  3737 
    Google Scholar
  • 5b Waser J. González-Gómez JC. Nambu H. Huber P. Carreira EM. Org. Lett.  2005,  7:  4249 
    Google Scholar
  • 6 For a review of reductive N-N bond cleavage of hydrazines, see: Gilchrist TL. In Comprehensive Organic Synthesis   Vol. 8:  Trost BM. Fleming I. Pergamon; Oxford: 1991.  p.388 ; see also ref. 5a
    Google Scholar
  • For reviews, see:
  • 7a Epsztein R. In Comprehensive Carbanion Chemistry   Chap. 3:  Buncel E. Durst T. Elsevier; New York: 1984.  p.107 
    Google Scholar
  • 7b Yamamoto H. In Comprehensive Organic Synthesis   Vol. 2:  Trost BM. Fleming I. Heathcock CH. Pergamon; Oxford: 1991.  p.81 
    Google Scholar