Download PDF
Synthesis 2009(14): 2467-2470  
DOI: 10.1055/s-0029-1216859
PSP
© Georg Thieme Verlag Stuttgart ˙ New York

Transition-Metal-Free Oxidative Homocoupling of Aryl, Alkenyl, and Alkynyl Grignard Reagents with TEMPO

Modhu Sudan Maji, Armido Studer*
Institute of Organic Chemistry, NRW Graduate School of Chemistry, Westfälische Wilhelms-University Münster, Corrensstr. 40, 48149 Münster, Germany
Fax: +49(251)8336523; e-Mail: studer@uni-muenster.de;
Further Information

Publication History

Received 18 March 2009
Publication Date:
29 May 2009 (online)

    Permissions and Reprints All articles of this category

Abstract

Oxidative homocoupling of aryl, alkenyl, and alkynyl Grignard reagents by using commercially available TEMPO as an organic oxidant is described. These coupling reactions occur highly efficiently without the presence of any transition metal.

Key words

Grignard reagents - oxidative homocoupling - alkoxyamine - nitroxide - persistent radicals

    References

  • 1a Whitesides GM. Newirth TL. J. Org. Chem.  1975,  40:  3448 
    Google Scholar
  • 1b Nagashima T. Curran DP. Synlett  1996,  330 
    Google Scholar
  • 1c Dalko PI. Tetrahedron Lett.  1999,  40:  4035 
    Google Scholar
  • 1d For organoboron compounds, see: Schaffner A.-P. Renaud P. Eur. J. Org. Chem.  2004,  2291 
    Google Scholar
  • 1e Review: Ollivier C. Renaud P. Chem. Rev.  2001,  101:  3415 
    Google Scholar
  • For reviews on the use of TEMPO in synthesis, see:
  • 2a Vogler T. Studer A. Synthesis  2008,  2163 
    Google Scholar
  • 2b Studer A. Schulte T. Chem. Rec.  2005,  5:  27 
    Google Scholar
  • 2c Studer A. Chem. Soc. Rev.  2004,  33:  267 
    Google Scholar
  • 2d Studer A. Chem. Eur. J.  2001,  7:  1159 
    Google Scholar
  • 2e For TEMPO as an oxidant in Rh-catalyzed processes, see: Vogler T. Studer A. Org. Lett.  2008,  10:  129 
    Google Scholar
  • 2f See also: Vogler T. Studer A. Adv. Synth. Catal.  2008,  350:  1963 
    Google Scholar
  • 2g For TEMPO as an oxidant in Pd-catalyzed CH arylations, see: Kirchberg S. Vogler T. Studer A. Synlett  2008,  2841 
    Google Scholar
  • 2h For TEMPO as an oxidant in biomimetic aldehyde oxidations, see: Guin J. De Sarkar S. Grimme S. Studer A. Angew. Chem. Int. Ed.  2008,  47:  8727 ; Angew. Chem. 2008, 120, 8855
    Google Scholar
  • 3 Maji MS. Pfeifer T. Studer A. Angew. Chem. Int. Ed.  2008,  47:  9547 ; Angew. Chem. 2008, 120, 9690
    CrossrefGoogle Scholar
  • 4 Hassan J. Sévignon M. Gozzi C. Schulz E. Lemaire M. Chem. Rev.  2002,  102:  1359 
    CrossrefPubMedGoogle Scholar
  • 5 Krasovskiy A. Tishkov A. del Amo V. Mayr H. Knochel P. Angew. Chem. Int. Ed.  2006,  45:  5010 ; Angew. Chem. 2006, 118, 5132
    CrossrefPubMedGoogle Scholar
  • 6 Watson SC. Eastham JF. J. Organomet. Chem.  1967,  9:  165 
    CrossrefGoogle Scholar
  • 7a Knochel P. Dohle W. Gommermann N. Kneisel FF. Kopp F. Korn T. Sapountzis I. Vu VA. Angew. Chem. Int. Ed.  2003,  42:  4302 ; Angew. Chem. 2003, 115, 4438
    Google Scholar
  • 7b Ren H. Krasovskiy A. Knochel P. Org. Lett.  2004,  6:  4215 
    Google Scholar
  • 8 For compounds 2a-c, 2e-j, 2o, and 2p, see: Miyake Y. Wu M. Rahman MJ. Kuwatani Y. Iyoda M. J. Org. Chem.  2006,  71:  6110 
    CrossrefGoogle Scholar
  • 9 For compound 2d, see: Li J.-H. Xie Y.-X. Yin D.-L. J. Org. Chem.  2003,  68:  9867 
    CrossrefPubMedGoogle Scholar
  • 10 For compounds 2m and 2n, see: Nising CF. Schmid UK. Nieger M. Bräse S. J. Org. Chem.  2004,  69:  6830 
    CrossrefGoogle Scholar
  • 11 For compound 2q, see: Zhang S. Zhang D. Liebeskind LS. J. Org. Chem.  1997,  62:  2312 
    CrossrefPubMedGoogle Scholar
  • 12 For compounds 2r-t and 2x, see: Li J. Liang Y. Xie Y. J. Org. Chem.  2005,  70:  4393 
    CrossrefPubMedGoogle Scholar
  • 13 For compound 2w, see: Blangetti M. Deagostino A. Rosso H. Prandi C. Zavattaro C. Venturello P. Eur. J. Org. Chem.  2007,  5867 
    CrossrefGoogle Scholar
  • 14 For compound 2u, see: Alonso DA. Nájera C. Pacheco MC. Adv. Synth. Catal.  2003,  345:  1146 
    CrossrefGoogle Scholar
  • 15 For compound 2v, see: Suzuki H. Aihara M. Yamamoto H. Takamoto Y. Ogawa T. Synthesis  1988,  236 
    Article in Thieme ConnectGoogle Scholar