Download PDF
Synthesis 2009(20): 3511-3518  
DOI: 10.1055/s-0029-1216987
SPECIALTOPIC
© Georg Thieme Verlag Stuttgart ˙ New York

C-H Bond Activation: A Versatile Protocol for the Direct Arylation and Alkenylation of Oxazoles

François Besselièvrea, Sabrina Lebrequierb, Florence Mahuteau-Betzerb, Sandrine Piguel*a
a Univ Paris-Sud 11, 91405 Orsay, France
Fax: +33(1)69075381; e-Mail: sandrine.piguel@curie.u-psud.fr;
b Institut Curie/CNRS, UMR176, Bât. 110, Centre Universitaire, 91405 Orsay, France
Further Information

Publication History

Received 29 March 2009
Publication Date:
03 September 2009 (online)

    Permissions and Reprints All articles of this category

Abstract

The versatile palladium complex Pd(PPh3)4 catalyses both direct arylation and alkenylation of oxazoles efficiently. The method is regioselective and stereospecific with respect to bromoalkenes and tolerates a wide range of functional groups.

Key words

oxazole - arylation - alkenylation - palladium - C-H activation

    References

  • For recent reviews of heteroarenes and arenes by direct arylation, see:
  • 1a Alberico D. Scott ME. Lautens M. Chem. Rev.  2007,  107:  174 
    Google Scholar
  • 1b Satoh T. Miura M. Chem. Lett.  2007,  36:  200 
    Google Scholar
  • 1c Seregin IV. Gevorgyan V. Chem. Soc. Rev.  2007,  36:  1173 
    Google Scholar
  • 1d Campeau L.-C. Stuart DR. Fagnou K. Aldrichimica Acta  2007,  40:  35 
    Google Scholar
  • 2 Turner GL. Morris JA. Greaney MF. Angew. Chem. Int. Ed.  2007,  46:  7996 
    CrossrefPubMedGoogle Scholar
  • 3 Ackermann L. Althammer A. Fenner S. Angew. Chem. Int. Ed.  2008,  48:  201 
    CrossrefGoogle Scholar
  • 4a Hachiya H. Hirano K. Satoh T. Miura M. Org. Lett.  2009,  11:  1737 
    Google Scholar
  • 4b Canivet J. Yamaguchi J. Ban I. Itami K. Org. Lett.  2009,  11:  1733 
    Google Scholar
  • 4c During the preparation of our manuscript, Itami published the first example of iridium-catalyzed direct arylation of azoles: Join B. Yamamoto T. Itami K. Angew. Chem. Int. Ed.  2009,  48:  3644 
    Google Scholar
  • For examples of direct arylation of benzoxazole derivatives, see:
  • 5a Lewis JC. Wu JY. Bergman RG. Ellman JA. Angew. Chem. Int. Ed.  2006,  45:  1589 
    Google Scholar
  • 5b Bellina F. Calandri C. Cauteruccio S. Rossi R. Tetrahedron  2007,  63:  1970 
    Google Scholar
  • 5c Do H.-Q. Daugulis O. J. Am. Chem. Soc.  2007,  129:  12404 ; and references cited therein
    Google Scholar
  • 5d Ferrer Flegeau E. Popkin ME. Greaney MF. Org. Lett.  2008,  10:  2717 ; and references cited therein
    Google Scholar
  • 5e Yoshizumi T. Satoh T. Hirano K. Matsuo D. Orita A. Otera J. Miura M. Tetrahedron Lett.  2009,  50:  3273 
    Google Scholar
  • 5f Verrier C. Martin T. Hoarau C. Marsais F. J. Org. Chem.  2008,  73:  7383 
    Google Scholar
  • 5g Nandurkar N. Bhanushali M. Malhari B. Bhanage B. Tetrahedron Lett.  2008,  49:  1045 
    Google Scholar
  • 5h For a mechanistic discussion, see: Sanchez RS. Zhuravlev A. J. Am. Chem. Soc.  2007,  129:  5824 
    Google Scholar
  • 5i Derridj F. Djebbar S. Benali-Baitich O. Doucet H. J. Organomet. Chem.  2008,  693:  135 
    Google Scholar
  • 5j Derridj F. Roger J. Geneste F. Djebbar S. Doucet H. J. Organomet. Chem.  2009,  694:  455 
    Google Scholar
  • 5k Ohnmacht SA. Mamone P. Culshaw AJ. Greaney MF. Chem. Commun.  2008,  1241 
    Google Scholar
  • 5l

    See also refs. 3, 4.

    Google Scholar
  • For examples of direct alkenylation of heteroarenes with alkenyl bromides, see:
  • 6a Oi S. Aizawa E. Ogino Y. Inoue Y. J. Org. Chem.  2005,  70:  3113 ; and references cited therein
    Google Scholar
  • 6b Zaitsev VG. Daugulis O. J. Am. Chem. Soc.  2005,  127:  4156 
    Google Scholar
  • 6c Gottumukkala AL. Derridj F. Djebbar S. Doucet H. Tetrahedron Lett.  2008,  49:  2926 
    Google Scholar
  • 6d Verrier C. Hoarau C. Marsais F. Org. Biomol. Chem.  2009,  647 
    Google Scholar
  • 6e Koubachi J. El Kazzouli S. Berteina Raboin S. Mouaddib A. Guillaumet G. Synthesis  2008,  2537 
    Google Scholar
  • 7 Palmer DC. Venkatraman S. In Oxazoles: Synthesis, Reactions and Spectroscopy, Part A   Wiley; Hoboken / NJ: 2004. 
    Google Scholar
  • 8 Besselièvre F. Mahuteau-Betzer F. Grierson D. Piguel S. J. Org. Chem.  2008,  73:  3278 
    CrossrefGoogle Scholar
  • 9 Besselièvre F. Piguel S. Mahuteau-Betzer F. Grierson D. Org. Lett.  2008,  10:  4029 
    CrossrefPubMedGoogle Scholar
  • 10a Do H.-Q. Daugulis O. J. Am. Chem. Soc.  2008,  130:  1128 
    Google Scholar
  • 10b Do H.-Q. Kashif Khan RM. Daugulis O. J. Am. Chem. Soc.  2008,  130:  15185 
    Google Scholar
  • 10c Yotphan S. Bergman R. Ellman J. Org. Lett.  2009,  11:  1511 
    Google Scholar
  • 10d See also: Sahnoun S. Messaoudi S. Peyrat JF. Brion JD. Alami M. Tetrahedron Lett.  2008,  49:  7279 
    Google Scholar
  • 11 Cheplogoi P. Mulholland D. Coombes P. Randrianarivelojosia M. Phytochemistry  2008,  69:  1384 
    CrossrefGoogle Scholar
  • 12 Unfortunately, these new conditions were not found to be applicable to related azoles such as benzothiazole, benzoxazole or caffeine
  • 13 Liégault B. Lapointe D. Caron L. Vlassova A. Fagnou K. J. Org. Chem.  2009,  74:  1826 
    CrossrefGoogle Scholar
  • 14 Coulson DR. Inorg. Synth.  1973,  13:  121 
    Google Scholar
  • 15 Nicolaou KC. Hao J. Reddy MV. Rao PB. Rassias G. Snyder SA. Huang X. Chen DY.-K. Brenzovich WE. Giuseppone N. Giannakakou P. O’Brate A. J. Am. Chem. Soc.  2004,  126:  12897 
    CrossrefPubMedGoogle Scholar
  • 16 Giddens A. Boshoff H. Franzblau S. Barry C. Copp B. Tetrahedron Lett.  2005,  46:  7355 
    CrossrefGoogle Scholar
  • 17 Schuh K. Glorius F. Synthesis  2007,  2297 
    Article in Thieme ConnectGoogle Scholar
  • 18 Zhang W. Shen G. Zhuang J. Zheng P. Ran X. J. Photochem. Photobiol., A  2002,  147:  25 
    Google Scholar
  • 19 Crowe E. Hossner F. Hughes M.-J. Tetrahedron  1995,  51:  8889 
    CrossrefGoogle Scholar
  • 20 Chudasama V. Wilden J. Chem. Commun.  2008,  3768 
    CrossrefGoogle Scholar