Download PDF
Synthesis 2008(20): 3267-3272  
DOI: 10.1055/s-2008-1067274
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Immobilization of NHC-Bearing Palladium Catalysts on Polyvinylpyridine; Applications in Suzuki-Miyaura and Hartwig-Buchwald Reactions under Batch and Continuous-Flow Conditions

Klaas Mennecke, Andreas Kirschning*
Institut für Organische Chemie, Leibniz Universität Hannover, Schneiderberg 1b, 30167 Hannover, Germany
Fax: +49(511)7623011; e-Mail: andreas.kirschning@oci.uni-hannover.de;
Further Information

Publication History

Received 3 June 2008
Publication Date:
25 September 2008 (online)

    Permissions and Reprints All articles of this category

Abstract

The facile coordinative immobilization of Organ’s PEPPSITM catalyst on a composite material composed of megaporous glass and polyvinylpyridine is described. The catalyst showed very good performance in Suzuki-Miyaura as well as Hartwig-Buchwald reactions of aryl chlorides under mild conditions and with low catalyst loadings. The modified PEPPSITM catalyst was probed both under batch mode and continuous-flow applications. The flow setup was also utilized to shed light on the stability of the PEPPSITM catalyst and the mobility of palladium.

Key words

microreactor - heterogeneous catalysis - Hartwig-Buchwald­ reaction - palladium - Suzuki-Miyaura reaction - immobilization

    References

  • 1a Metal-Catalyzed Cross-Coupling Reactions   de Meijere A. Diederich F. Wiley-VCH; Weinheim: 2004.  2nd ed..
    Google Scholar
  • 1b Handbook of Organopalladium Chemistry for Organic Synthesis   Negishi E. Wiley; New York: 2002. 
    Google Scholar
  • 2a Hermann WA. Angew. Chem. Int. Ed.  2002,  41:  1290 ; Angew. Chem. 2002, 114, 1342
    Google Scholar
  • 2b Perry MC. Burgess K. Tetrahedron: Asymmetry  2003,  14:  951 
    Google Scholar
  • 2c Peris E. Crabtree RH. Coord. Chem. Rev.  2004,  248:  2239 
    Google Scholar
  • 2d Crudden CM. Allen DP. Coord. Chem. Rev.  2004,  248:  2247 
    Google Scholar
  • 2e Hermann WA. Öffle K. v. Preysing D. Schneider KS. J. Organomet. Chem.  2003,  687:  229 
    Google Scholar
  • 2f Jackstell R. Andreu MG. Frisch AC. Selvakumar K. Zapf A. Klein H. Spannenberg A. Röttger D. Briel O. Karch R. Beller M. Angew. Chem. Int. Ed.  2002,  41:  986 ; Angew. Chem. 2002, 114, 1028
    Google Scholar
  • 2g Gstöttmayr CWK. Böhm VPW. Herdtweck E. Grosche M. Herrmann WA. Angew. Chem. Int. Ed.  2002,  41:  1363 ; Angew. Chem. 2002, 114, 1421
    Google Scholar
  • 2h Lebel H. Janies MK. Charette AB. Nolan SP. J. Am. Chem. Soc.  2004,  126:  5046 
    Google Scholar
  • 2i Jensen DR. Schlutz MJ. Mueller JA. Sigman MS. Angew. Chem. Int. Ed.  2003,  42:  3810 ; Angew. Chem. 2003, 115, 3940
    Google Scholar
  • Reviews on immobilized catalysts:
  • 3a Immobilized Catalysts: Kirschning A. Top. Curr. Chem.  2004,  242 
    Google Scholar
  • 3b Solodenko W. Frenzel T. Kirschning A. In Polymeric Materials in Organic Synthesis and Catalysis   Buchmeiser MR. Wiley-VCH; Weinheim: 2003.  p.201 
    Google Scholar
  • Recoverable catalysts and reagents:
  • 3c Gladysz JA. Chem. Rev.  2002,  102:  3215 
    Google Scholar
  • 3d McNamara CA. Dixon MJ. Bradley M. Chem. Rev.  2002,  102:  3275 
    Google Scholar
  • 4 Kirschning A. Solodenko W. Mennecke K. Chem. Eur. J.  2006,  12:  5972 
    CrossrefPubMedGoogle Scholar
  • 5a Mennecke K. Grela K. Kunz U. Kirschning A. Synlett  2005,  2948 
    Google Scholar
  • 5b Solodenko W. Mennecke K. Vogt C. Gruhl S. Kirschning A. Synthesis  2006,  1873 
    Google Scholar
  • 5c Michrowska A. Mennecke K. Kunz U. Kirschning A. Grela K. J. Am. Chem. Soc.  2006,  128:  13267 
    Google Scholar
  • 6a Hadei N. Kantchev EAB. O’Brien CJ. Organ MG. Org. Lett.  2005,  7:  1991 
    Google Scholar
  • 6b Organ MG. Avola S. Dubovyk I. Hadei N. Kantchev EAB. O’Brien CJ. Valente C. Chem. Eur. J.  2006,  12:  4749 
    Google Scholar
  • 6c O’Brien CJ. Kantchev EAB. Valente C. Hadei N. Chass GA. Lough A. Hopkinson AC. Organ MG. Chem. Eur. J.  2006,  12:  4743 
    Google Scholar
  • 6d Assen E. Kantchev EAB. O’Brien CJ. Organ MG. Angew. Chem. Int. Ed.  2007,  46:  2768 ; Angew. Chem. 2007, 119, 2824
    Google Scholar
  • 7a Kunz U. Kirschning A. Altwicker C. Solodenko W. J. Chromatogr., A  2003,  1006:  241 
    Google Scholar
  • 7b Kunz U. Kirschning A. Wen H.-L. Solodenko W. Cecillia R. Kappe CO. Turek T. Catal. Today  2005,  105:  318 
    Google Scholar
  • 7c Kunz U. Schönfeld H. Solodenko W. Jas G. Kirschning A. Ind. Eng. Chem. Res.  2005,  44:  8458 
    Google Scholar
  • 7d Yamada YMA. Takeda K. Takahashi H. Ikegami S. J. Org. Chem.  2003,  68:  7733 
    Google Scholar
  • 8 Kirschning A. Altwicker C. Dräger G. Harders J. Hoffmann N. Hoffmann U. Schönfeld H. Solodenko W. Kunz U. Angew. Chem. Int. Ed.  2001,  40:  3995 ; Angew. Chem. 2001 , 113, 4118
    CrossrefGoogle Scholar
  • 9 Baxendale IR. Griffiths-Jones CM. Ley SV. Trammer GK. Chem. Eur. J.  2006,  12:  4407 
    CrossrefGoogle Scholar
  • 10 Kirschning A. Mennecke K. Solodenko W. Synthesis  2008,  1589 
    Article in Thieme ConnectGoogle Scholar
  • 11a Buchwald SL. Jiang L. In Metal-Catalyzed Cross-Coupling Reactions   2nd ed., Vol. 2:  de Meijere A. Diederich F. Wiley-VCH; Weinheim: 2004.  p.699-760  
    Google Scholar
  • 11b Shen Q. Hartwig JF. J. Am. Chem. Soc.  2006,  128:  10028 
    Google Scholar
  • 12a Parrish CA. Buchwald SL. J. Org. Chem.  2001,  66:  3820 
    Google Scholar
  • 12b For homogeneous catalysis see: Schlummer B. Scholz U. Adv. Synth. Catal.  2004,  346:  1599 
    Google Scholar
  • 13a Seganish WM. DeShong P. Org. Lett.  2004,  6:  4379 
    Google Scholar
  • 13b Alonso DA. Nájera C. Pacheco MC. J. Org. Chem.  2002,  67:  5588 
    Google Scholar
  • 13c Wang L. Zhang Y. Liu L. Wang Y. J. Org. Chem.  2006,  71:  1284 
    Google Scholar
  • 13d Urgaonkar S. Verkade JG. J. Org. Chem.  2004,  69:  9135 
    Google Scholar
  • 13e Marion N. Navarro O. Mei J. Stevens ED. Scott NM. Nolan SP. J. Am. Chem. Soc.  2006,  128:  4101 
    Google Scholar
  • 13f Belfield AJ. Brown GR. Foubister AJ. Ratcliffe PD. Tetrahedron  1999,  55:  13285 
    Google Scholar
  • 13g Okano K. Tokuyama H. Fukuyama T. Org. Lett.  2003,  5:  4987 
    Google Scholar