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Synthesis 2010(14): 2379-2382  
DOI: 10.1055/s-0029-1220011
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Halofluorination of Alkenes Using Trihaloisocyanuric Acids and HF×Pyridine

Lívia T. C. Crespo, Rodrigo da S. Ribeiro, Marcio C. S. de Mattos*, Pierre M. Esteves*
Instituto de Química, Departamento de Química Orgânica, Universidade Federal do Rio de Janeiro, Cx Postal 68545, 21945-970, Rio de Janeiro, Brazil
Fax: +55(21)25627256; e-Mail: pesteves@iq.ufrj.br; e-Mail: mmattos@iq.ufrj.br;
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Publication History

Received 29 January 2010
Publication Date:
18 May 2010 (online)

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Abstract

Halofluorination of alkenes with a new system (trihaloisocyanuric acids and HF˙pyridine) results in the formation of vicinal halofluoroalkanes. The reaction is regioselective leading to Markovnikov-oriented products and the halofluorinated adducts follow anti-addition in the case of cyclohexene and 1-methylcyclohexene. Reaction yields range from 67-88%.

Key words

electrophilic addition - halogenation - alkenes - halides - regioselectivity

    References

  • 1a Chambers RD. Fluorine in Organic Chemistry   Blackwell; Oxford: 2004. 
    Google Scholar
  • 1b Kirsch P. Modern Fluoroorganic Chemistry: Synthesis, Reactivity, Applications   Wiley-VCH; Weinheim: 2004. 
    Google Scholar
  • 1c O’Hagan D. Chem. Soc. Rev.  2008,  37:  308 
    Google Scholar
  • 1d Smart BE. J. Fluorine Chem.  2001,  109:  3 
    Google Scholar
  • 1e Yoshino H. Matsumoto K. Hagiwara R. Ito Y. Oshima K. Matsubara S. J. Fluorine Chem.  2006,  127:  29 
    Google Scholar
  • 2a Wilkinson JA. Chem. Rev.  1992,  92:  505 
    Google Scholar
  • 2b Dolbier WR. J. Fluorine Chem.  2005,  126:  157 
    Google Scholar
  • 2c Mikami K. Itoh Y. Yamanaka M. Chem. Rev.  2004,  104:  1 
    Google Scholar
  • 2d Bégué J.-P. Bonnet-Delpon D. J. Fluorine Chem.  2006,  127:  992 
    Google Scholar
  • 3 Purser S. Moore PR. Swallow S. Gouverneur V. Chem. Soc. Rev.  2008,  37:  320 
    CrossrefPubMedGoogle Scholar
  • 4 Lübke M. Skupin R. Haufe G. J. Fluorine Chem.  2000,  102:  125 
    CrossrefGoogle Scholar
  • 5a Olah GA. Nojima M. Kerekas I. Synthesis  1973,  780 
    Google Scholar
  • 5b Olah GA. Welch JT. Vankar YD. Nojima M. Kerekes I. Olah JA. J. Org. Chem.  1979,  44:  3872 
    Google Scholar
  • 5c Haufe G. Alvernhe G. Laurent A. Tetrahedron Lett.  1986,  27:  4449 
    Google Scholar
  • 5d Hedhli A. Baklouti A. J. Org. Chem.  1994,  59:  5277 
    Google Scholar
  • 5e Haufe G. Webel U. Schulze K. Alvernhe G. J. Fluorine Chem.  1995,  74:  283 
    Google Scholar
  • 5f Kremlev MM. Haufe G. J. Fluorine Chem.  1998,  90:  121 
    Google Scholar
  • 5g Dolensky B. Kirk KL. J. Org. Chem.  2002,  67:  3468 
    Google Scholar
  • 5h Haufe G. Alvernhe G. Laurent A. Ernet T. Goj O. Kröger S. Sattler A. Org. Synth. Coll. Vol. 10   Wiley; New York: 2004.  p.128 
    Google Scholar
  • 5i O’Hagan D. Rzepa HS. Schüler M. Slawin AMZ. Beilstein J. Org. Chem.  2006,  2:  19 
    Google Scholar
  • 5j Dolenc D. Sket B. Synlett  1995,  327 
    Google Scholar
  • 5k Camps F. Chamorro E. Gasol V. Guerrero A. J. Org. Chem.  1989,  54:  4294 
    Google Scholar
  • 5l Yoshino H. Matsubara S. Oshima K. Matsumoto K. Hagiwara R. Ito Y. J. Fluorine Chem.  2005,  126:  121 
    Google Scholar
  • 5m Albanese D. Landini D. Penso M. Pratelli M. Gazz. Chim. Ital.  1991,  121:  537 
    Google Scholar
  • 5n Dolenc D. Synlett  2000,  544 
    Google Scholar
  • 5o Chi DY. Lidström PJ. Choe YS. Bonasera TA. Welch MJ. Katzenellenbogen JA. J. Fluorine Chem.  1995,  71:  143 
    Google Scholar
  • 5p Zupan M. Pollak A. J. Chem. Soc., Perkin Trans. 1  1976,  971 
    Google Scholar
  • 6a Mendonça GF. De Mattos MCS. Quim. Nova  2008,  31:  798 
    Google Scholar
  • 6b Mendonça GF. Magalhaes RR. De Mattos MCS. Esteves PM. J. Braz. Chem. Soc.  2005,  16:  695 
    Google Scholar
  • 6c Mendonça GF. Sanseverino AM. De Mattos MCS. Synthesis  2003,  45 
    Google Scholar
  • 7a De Almeida LS. Esteves PM. De Mattos MCS. Synthesis  2006,  221 
    Google Scholar
  • 7b De Almeida LS. Esteves PM. De Mattos MCS. Synlett  2006,  1515 
    Google Scholar
  • 8a Ribeiro R. da S. Esteves PM. De Mattos MCS. Tetrahedron Lett.  2007,  48:  8747 
    Google Scholar
  • 8b Ribeiro R. da S. Esteves PM. De Mattos MCS. J. Braz. Chem. Soc.  2008,  19:  1239 
    Google Scholar
  • 9 Trost BM. Science  1991,  254:  1471 
    Google Scholar
  • 10 Tozetti SDF. De Almeida LS. Esteves PM. De Mattos MCS. J. Braz. Chem. Soc.  2007,  18:  675 
    CrossrefGoogle Scholar
  • 11 Allyl and vinyl chlorides were also formed in the reaction of α-methylstyrene with NCS: Reed SF. J. Org. Chem.  1965,  30:  3258 
    Google Scholar