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Synthesis 2005(4): 547-550  
DOI: 10.1055/s-2005-861791
PAPER
© Georg Thieme Verlag Stuttgart · New York

The Conversion of Phenols to the Corresponding Aryl Halides Under Mild Conditions

Alicia L. S. Thompsona, George W. Kabalkab, Murthy R. Akulab, John W. Huffman*a
a Clemson University, Department of Chemistry, Clemson, South Carolina 29634-0973, USA
Fax: +1(864)6566613; e-Mail: huffman@clemson.edu;
b Departments of Chemistry and Radiology, The University of Tennessee, Knoxville, Tennessee 37996-1600, USA
Further Information

Publication History

Received 23 July 2004
Publication Date:
18 January 2005 (online)

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Abstract

Mild, novel procedures have been developed for the syntheses of aryl halides from the corresponding phenols in modest to good yields via boronate ester intermediates.

Key words

aryl halides - phenols - boronates - halogenation - palladium coupling

    References

  • 1 Johnson MR. Melvin LS. In Cannabinoids as Therapeutic Agents   Mechoulam R. CRC Press; Boca Raton: 1986.  p.121-145  
    Google Scholar
  • 2 Huffman JW. Liddle J. Yu S. Aung MM. Abood ME. Wiley JL. Martin BR. Bioorg. Med. Chem.  1999,  7:  2095 
    CrossrefGoogle Scholar
  • 3 Thompson, A. L. S., unpublished work.
  • 4a Dominianni SJ. Ryan CW. De Armitt CW. J. Org. Chem.  1977,  42:  344 
    CrossrefGoogle Scholar
  • 4b Huffman JW. Joyner HH. Lee MD. Jordan RD. Pennington WT. J. Org. Chem.  1991,  56:  2081 
    CrossrefGoogle Scholar
  • 5a Bay E. Bak DA. Timony PE. Leone-Bay A. J. Org. Chem.  1990,  55:  3415 
    Google Scholar
  • 5b Bestman HJ. Schnabel KH. Justus Liebigs Ann. Chem.  1966,  698:  106 
    Google Scholar
  • 5c Wiley GA. Hershkowitz RL. Rein BM. Chung BC. J. Am. Chem. Soc.  1964,  86:  964 
    Google Scholar
  • 5d Albert A. Clarke J. J. Chem. Soc.  1964,  1666 
    Google Scholar
  • 5e Park JD. Rosser RW. Lacher JR. J. Org. Chem.  1962,  27:  1462 
    Google Scholar
  • 5f Cramer R. Coffman DD. J. Org. Chem.  1961,  26:  4164 
    Google Scholar
  • 5g Price CC. Roberts EM. Org. Synth. Coll. Vol III   Wiley; New York: 1955.  p.272 
    Google Scholar
  • 5h Bendich A. Russell PJ. Fox JJ. J. Am. Chem. Soc.  1954,  76:  6073 
    Google Scholar
  • 5i Surrey AR. Cutler RA. J. Am. Chem. Soc.  1954,  76:  1109 
    Google Scholar
  • 5j Baddiley J. Topham A. J. Chem. Soc.  1944,  678 
    Google Scholar
  • 6 Murata M. Oyama T. Watanabe W. Masuda Y. J. Org. Chem.  2000,  65:  164 
    CrossrefGoogle Scholar
  • 7 Kabalka GW. Akula MR. Zhang J. Nucl. Med. Biol.  2002,  29:  841 
    CrossrefGoogle Scholar
  • 8 Kabalka GW. Sastry KAR. Sastry U. Somayaji V. Org. Prep. Proced. Int.  1982,  14:  359 
    CrossrefGoogle Scholar
  • 10 Nesmejanow AN. Perewalowa EG. Jurjewa LP. Chem. Ber.  1960,  2729 
    Google Scholar
  • For selected examples of experimental methods for the preparation of trifluoromethanesulfonates, see:
  • 11a Ritter K. Synthesis  1993,  735 
    Google Scholar
  • 11b Stang PJ. Hanack M. Subramanian LR. Synthesis  1982,  85 
    Google Scholar
  • 11c Echavarren AM. Stille JK. J. Am. Chem. Soc.  1987,  109:  5478 
    Google Scholar
  • 11d Tilley JW. Danho W. Lovey K. Wagner R. Swistok J. Makofske R. Michalewsky J. Triscari J. Nelson D. Weatherford S. J. Med. Chem.  1991,  34:  1125 
    Google Scholar
  • 11e Rudisill DE. Stille JK. J. Org. Chem.  1989,  54:  5856 
    Google Scholar
  • 12 Kaliakoudas D. Eugster CH. Ruedi P. Helv. Chim. Acta  1990,  73:  48 
    CrossrefGoogle Scholar
  • 13a Harayama T. Nakatsuka K. Nishioka H. Murakami K. Hayashida N. Ishii H. Chem. Pharm. Bull.  1994,  42:  2170 
    CrossrefGoogle Scholar
  • 13b Mitteilung K. Reisch J. Rosenthal BHW. Monatsh. Chem.  1987,  118:  871 
    CrossrefGoogle Scholar
  • 14 Sukman EL. inventors; U.S. Patent,  4264593.  ; no spectroscopic data are included in this patent
  • 15 Barluenga J. Campos PJ. Gonzalez JM. Asensio G. J. Chem. Soc, Perkin Trans. 1  1984,  2623 
    CrossrefGoogle Scholar
9

Pinacolboronates 6 could be converted to the corresponding boronic acid using NaIO4 and NH4OAc. The boronic acids were then converted to the aryl bromide under the conditions described in ref.7 The overall yields for this procedure were inferior to those developed subsequently.