Download PDF
Synlett 2003(8): 1145-1148
DOI: 10.1055/s-2003-39887
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Fast and Easy Halide Exchange in Aryl Halides

Riina K. Arvela, Nicholas E. Leadbeater*
Department of Chemistry, King’s College London, Strand, London, WC2R 2LS, UK
Fax: +44(20)78482810; e-Mail: nicholas.leadbeater@kcl.ac.uk;
Further Information

Publication History

Received 26 March 2003
Publication Date:
11 June 2003 (online)

    Permissions and Reprints All articles of this category

Abstract

We report here the rapid halide exchange in aryl halides facilitated by microwave and conventional heating using nickel(II) halides as reagents. The methodology can be used for conversion of aryl chlorides to bromides, aryl iodides to bromides and chlorides and aryl bromides to chlorides. Reactions are fast (5 minutes reaction time for microwave heating and 4 hours for conventional heating) and can be performed without the need for exclusion of air and water.

Key words

aryl halide - nickel - water - microwave

    References

  • 1 Metal-Catalysed Cross-Coupling Reactions   Diederich F. Stang PJ. Wiley-VCH; New York: 1998. 
    Google Scholar
  • For recent reviews see:
  • 2a Hassan J. Sévignon M. Gozzi C. Schulz E. Lemaire M. Chem. Rev.  2002,  102:  1359 
    Google Scholar
  • 2b Suzuki A. J. Organomet. Chem.  1999,  576:  147 
    Google Scholar
  • 2c Miyaura N. Suzuki A. Chem. Rev.  1995,  95:  2457 
    Google Scholar
  • 3 See for example: Kashiyama E. Hutchinson I. Chua M.-S. Stinson SF. Phillips LR. Kaur G. Sauville EA. Bradshaw TD. Westwell AD. Stevens MFG. J. Med. Chem.  1999,  42:  4172 
    CrossrefGoogle Scholar
  • 4 Leadbeater NE. Marco M. Org. Lett.  2002,  4:  2973 
    CrossrefGoogle Scholar
  • 5 Leadbeater NE. Marco M. J. Org. Chem.  2003,  68:  888 
    CrossrefGoogle Scholar
  • 6 Bacon RGR. Hill HAO. J. Chem. Soc.  1964,  1097 
    Google Scholar
  • 7 Clark JH. Denness JE. McClinton MA. Wynd AJ. J. Fluorine Chem.  1990,  50:  411 
    Google Scholar
  • 8 Bozell JJ. Vogt CE. J. Am. Chem. Soc.  1988,  110:  2655 
    CrossrefGoogle Scholar
  • 9 Yang SH. Li CS. Cheng CH. J. Org. Chem.  1987,  52:  691 
    CrossrefGoogle Scholar
  • 10 Takagi K. Hayama N. Inokawa S. Bull. Chem. Soc. Jpn.  1980,  53:  3691 
    Google Scholar
  • 11 O’Connor KJ. Burrows CJ. J. Org. Chem.  1991,  56:  1344 
    Google Scholar
  • 12a Arnold JT. Bayraktaroglu TO. Brown RG. Heiermann CR. Magnus WW. Ohman AB. Landolt RG. J. Org. Chem.  1992,  57:  391 
    Google Scholar
  • 12b Bayraktaroglu TO. Gooding MA. Khatib SF. Lee H. Kourouma M. Landolt RG. J. Org. Chem.  1993,  58:  1264 
    Google Scholar
  • 13a Vol S. Vivier L. Pérot G. J. Mol. Catal. A.: Chem.  2001,  172:  241 
    CrossrefGoogle Scholar
  • 13b Imhaoulene S. Vivier L. Guisnet M. Pérot G. Tetrahedron  1994,  50:  12913 
    CrossrefGoogle Scholar
  • 14 Meyer G. Rollin Y. Perichon J. Tetrahedron Lett.  1986,  27:  3497 
    Google Scholar
  • 15 Bonnichon F. Grabner G. Guyot G. Richard C. J. Chem. Soc., Perkin Trans. 2  1999,  1203 
    Google Scholar
  • 16 Klapars A. Buchwald SL. J. Am. Chem. Soc.  2002,  124:  14844 
    CrossrefPubMedGoogle Scholar
  • For recent reviews on the area, see:
  • 17a Larhed M. Moberg C. Hallberg A. Acc. Chem. Res.  2002,  35:  717 
    CrossrefGoogle Scholar
  • 17b Lew A. Krutzik PO. Hart ME. Chamberlin AR. J. Comb. Chem.  2002,  4:  95 
    CrossrefGoogle Scholar
  • 17c Lindström P. Tierney J. Wathey B. Westman J. Tetrahedron  2001,  57:  9225 
    CrossrefGoogle Scholar
  • 18 For a review on the concepts, see: Gabriel C. Gabriel S. Grant EH. Halstead BS. Mingos DMP. Chem. Soc. Rev.  1998,  27:  213 
    CrossrefGoogle Scholar
19

Yields for the transformation with other solvents: H2O, 0%, PEG-400, 8%, DME, 0%.

20

CAUTION: The DMF is heated above its boiling point so all necessary precautions should be taken when performing such experiments. Vessels designed to withhold elevated pressures must be used. The microwave apparatus used here incorporates a protective metal cage around the microwave vessel in case of explosion. After completion of an experiment, the vessel must be allowed to cool to a temperature below the boiling point of the solvent before removal from the microwave cavity and opening to the atmosphere.

21

CAUTION: A blast shield should be in place and vessels designed to withhold elevated pressures must be used. After completion of an experiment, the vessel must be allowed to cool before opening to the atmosphere.