Download PDF
Synlett 2002(2): 0273-0274
DOI: 10.1055/s-2002-19775
LETTER
© Georg Thieme Verlag Stuttgart · New York

A Practical Synthesis of Pyridylboranes via Magnesium-Halogen Exchange

Weiling Cai, David H. Brown Ripin*
Process Research and Development, Central Research Division, Pfizer Inc., Eastern Point Road, Groton, Connecticut 06340, USA
Fax: +1(860)4413630; e-Mail: David_B_Ripin@groton.pfizer.com;
Further Information

Publication History

Received 11 November 2001
Publication Date:
02 February 2007 (online)

    Permissions and Reprints All articles of this category

Abstract

Dialkylpyridylboranes can be prepared by the reaction of the corresponding pyridylmagnesium chloride with diethylmethoxyborane at 0-25 °C. The pyridylmagnesium chlorides are generated from the corresponding bromopyridines via magnesium-halogen exchange reaction.

Key words

magnesium halogen exchange - pyridylborane - Grignard reagent - metalation

    References

  • 1 Li JJ. Gribble GW. Palladium in Heterocyclic Chemistry   Pergamon; Oxford: 2000. 
    Google Scholar
  • 2a Ishikura M. Mano T. Oda I. Terashima M. Heterocycles  1984,  22:  2471 
    CrossrefGoogle Scholar
  • 2b Ishikura M. Ohta T. Terashima M. Chem. Pharm. Bull.  1983,  31:  4573 
    CrossrefGoogle Scholar
  • 2c Morris GA. Nguyen ST. Tetrahedron Lett.  2001,  42:  2093 
    CrossrefGoogle Scholar
  • 2d Labadie SS, Rotstein DM, Sjogren EB, and Talamas FX. inventors; World Patent,  9957101. 
    Crossref
  • 3a Gilman H. Spatz SM. J. Org. Chem.  1951,  16:  1485 
    CrossrefGoogle Scholar
  • 3b Mallet M. Branger G. Marsaia F. Quenguiner G. J. Organomet. Chem.  1990,  382:  319 
    CrossrefGoogle Scholar
  • 4a Harris SA. Iowa State Coll. J. Sci.  1932,  6:  425 
    Google Scholar
  • 4b Overhoff J. Proost W. Rec. Trav. Chim.  1938,  57:  179 
    Google Scholar
  • 4c Proost W. Wibaut JP. Rec. Trav. Chim.  1940,  59:  971 
    Google Scholar
  • 4d Lai Y.-H. Synthesis  1981,  585 
    Google Scholar
  • 4e Nakane M. Hutchinson CR. J. Org. Chem.  1978,  43:  3922 
    Google Scholar
  • Magnesium halogen exchange:
  • 5a Abarbri M. Thibonnet J. Berillon L. Dehmel F. Rottlaender M. Knochel P. J. Org. Chem.  2000,  65:  4618 
    Google Scholar
  • 5b Rottlander M. Boymond L. Berillon L. Lepretre A. Varchi G. Avolio S. Laaziri H. Queguiner G. Ricci A. Cahiez G. Knochel P. Chem.- Eur. J.  2000,  6:  767 
    Google Scholar
  • 5c Lepretre A. Turck A. Ple N. Knochel P. Queguiner G. Tetrahedron  2000,  56:  265 
    Google Scholar
  • 5d Shimura A. Momotake A. Togo H. Yokoyama M. Synthesis  1999,  495 
    Google Scholar
  • 5e Kondo Y. Yoshida A. Sato S. Sakamoto T. Heterocycles  1996,  42:  105 
    Google Scholar
  • 5f Turner RM. Lindell SD. Ley SV. J. Org. Chem.  1991,  56:  5739 
    Google Scholar
  • 5g Abarbri M. Dehmel F. Knochel P. Tetrahedron Lett.  1999,  40:  7449 
    Google Scholar
  • 5h Dehmel F. Abarbri M. Knochel P. Synlett.  2000,  345 
    Google Scholar
  • 5i Felding J. Kristensen J. Bjerregaard T. Sander L. Vedso P. Begtrup M. J. Org. Chem.  1999,  64:  41964 
    Google Scholar
  • 6 Pyridyl Grignard reagents have also been generated by ligand exchange reactions of aryl pyridyl sulfoxides with Grignard reagents: Shibutani T. Fujihara H. Furukawa N. Heteroat. Chem.  1991,  2:  521 
    CrossrefGoogle Scholar
  • 7a Paradies HH. Gorbing M. Angew. Chem. Int. Ed. Engl.  1969,  8:  279 
    CrossrefGoogle Scholar
  • 7b Martin GJ. Mechin B. Leroux Y. Paulmier C. Meunier JC. J. Organomet. Chem.  1974,  67:  327 
    CrossrefGoogle Scholar
  • 7c Furukawa N. Shibutani T. Fujihara H. Tetrahedron Lett.  1987,  28:  5845 
    CrossrefGoogle Scholar
  • 7d Trecourt F. Breton G. Bonnet V. Mongin F. Marsais F. Queguiner G. Tetrahedron Lett.  1999,  40:  4339 
    CrossrefGoogle Scholar
  • 7e Berillon L. Lepretre A. Turck A. Ple N. Queguiner G. Cahiez G. Knochel P. Synlett  1998,  1359 
    CrossrefGoogle Scholar
  • 7f Trecourt F. Breton G. Bonnet V. Mongin F. Marsais F. Queguiner G. Tetrahedron  2000,  56:  1349 
    CrossrefGoogle Scholar
8

All products have been fully characterized by spectroscopic methods after isolation by crystallization.