Download PDF
Synlett 2011(17): 2545-2550  
DOI: 10.1055/s-0030-1260322
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

A Highly Sustainable and Active Catalyst for Suzuki-Miyaura Reaction: Palladium-Supported Ionic Liquid Catalyst (SILC) Coated with Polymer

Hisahiro Hagiwara*a, Kota Satoa, Takashi Hoshib, Toshio Suzukib
a Graduate School of Science and Technology, Niigata University, 8050, 2-Nocho, Ikarashi, Nishi-ku, Niigata 950-2181, Japan
Fax: +81252627368; e-Mail: hagiwara@gs.niigata-u.ac.jp;
b Faculty of Engineering, Niigata University, 8050, 2-Nocho, Ikarashi, Nishi-ku, Niigata 950-2181, Japan
Further Information

Publication History

Received 16 July 2011
Publication Date:
22 September 2011 (online)

    Permissions and Reprints All articles of this category

Corrected by:

A Highly Sustainable and Active Catalyst for Suzuki-Miyaura Reaction: Palladium-Supported Ionic Liquid Catalyst (SILC) Coated with PolymerSynlett 2011; 2011(19): 2905-2905
DOI: 10.1055/s-0031-1289895

Abstract

With the aid of an ionic liquid, palladium acetate was immobilized in the pores of silica gel, which was coated with polyethylene terephthalate. The heterogeneous catalyst was effective for Suzuki-Miyaura reactions of ortho-substituted aryl bromides, aryl triflates, and arylboronic acids in aqueous ethanol at room temperature, and could be re-used up to ten times.

Key words

catalysis - green chemistry - heterogeneous catalysis - palladium - supported catalysis

    References and Notes

  • 1 Ionic Liquids in Synthesis   2nd ed.:  Wasserscheid P. Welton T. Wiley-VCH; Weinheim: 2008. 
    Google Scholar
  • For recent advances on SILC, see:
  • 2a Mehnert CP. Mozeleski EJ. Cook RA. Chem. Commun.  2002,  3010 
    Google Scholar
  • 2b Riisager A. Wasserscheid P. van Hal R. Fehrmann R. J. Catal.  2003,  219:  452 
    Google Scholar
  • 2c Huang J. Jiang T. Gao H. Han B. Liu Z. Wu W. Chang Y. Zhao G. Angew. Chem. Int. Ed.  2004,  43:  1397 
    Google Scholar
  • 2d Breitenlechner S. Fleck M. Müller TE. Suppan A. J. Mol. Catal. A: Chem.  2004,  214:  175 
    Google Scholar
  • 2e Riisager A. Fehrmann R. Flicker S. van Hal R. Hanmann M. Wasserscheid P. Angew. Chem. Int. Ed.  2005,  44:  815 
    Google Scholar
  • 2f Mehnert CP. Chem. Eur. J.  2005,  11:  50 
    Google Scholar
  • 2g Lou L.-L. Yu K. Ding F. Thou W. Peng X. Liu S. Tetrahedron Lett.  2006,  47:  6513 
    Google Scholar
  • 2h Kernchen U. Etzol B. Korth W. Jess A. Chem. Eng. Technol.  2007,  30:  985 
    Google Scholar
  • 2i Rodriguez-Perez L. Teuma F. Falqui A. Goomez M. Serp P. Chem. Commun.  2008,  4201 
    Google Scholar
  • 2j Gu Y. Li G. Adv. Synth. Catal.  2009,  351:  817 
    Google Scholar
  • 3a Hagiwara H. Sugawara Y. Isobe K. Hoshi T. Suzuki T. Org. Lett.  2004,  6:  2325 
    Google Scholar
  • 3b Hagiwara H. Sugawara Y. Hoshi T. Suzuki T. Chem. Commun.  2005,  2942 
    Google Scholar
  • 4a Hagiwara H. Ko KH. Hoshi T. Suzuki T. Chem. Commun.  2007,  2838 
    Google Scholar
  • 4b Hagiwara H. Sasaki H. Tsubokawa N. Hoshi T. Suzuki T. Tsuda T. Kuwabata S. Synlett  2010,  1990 
    Google Scholar
  • 5 Hagiwara H. Nakamura T. Hoshi T. Suzuki T. Green Chem.  2011,  13:  1133 
    CrossrefGoogle Scholar
  • 6 Hagiwara H. Sasaki H. Hoshi T. Suzuki T. Synlett  2009,  643 
    Article in Thieme ConnectGoogle Scholar
  • 7a Hagiwara H. Okunaka N. Hoshi T. Suzuki T. Synlett  2008,  1813 
    Google Scholar
  • 7b Hagiwara H. Nakamura T. Okunaka N. Hoshi T. Suzuki T. Helv. Chim. Acta  2010,  93:  175 
    Google Scholar
  • 8 Hagiwara H. Kuroda T. Hoshi T. Suzuki T. Adv. Synth. Catal.  2010,  352:  909 
    CrossrefGoogle Scholar
  • For recent reviews on Suzuki-Miyaura reaction, see:
  • 9a Miyaura N. Suzuki A. Chem. Rev.  1995,  95:  2457 
    Google Scholar
  • 9b Littke AF. Fu GC. Angew. Chem. Int. Ed.  2002,  41:  4176 
    Google Scholar
  • 9c Miyaura N. Top. Curr. Chem.  2002,  219:  11 
    Google Scholar
  • 9d Hassan J. Sevignon M. Gozzi C. Schulz E. Lemaire M. Chem. Rev.  2002,  102:  1359 
    Google Scholar
  • 9e Kotha S. Lahiri K. Kashinath D. Tetrahedron  2002,  58:  9633 
    Google Scholar
  • 9f Bellina F. Carpita A. Rossi R. Synthesis  2004,  2419 
    Google Scholar
  • 9g Alonso F. Beletskaya LP. Yus M. Tetrahedron  2008,  64:  3047 
    Google Scholar
  • 9h Martin R. Buchwald SL. Acc. Chem. Res.  2008,  41:  1461 
    Google Scholar
  • 10 Rouhi AM. Chem. Eng. News  2004,  82:  49 
    Google Scholar
  • 11 Hoshi T. Saitoh I. Nakazawa T. Suzuki T. Sakai J.-I. Hagiwara H. J. Org. Chem.  2009,  74:  4013 ; and earlier references cited therein
    CrossrefGoogle Scholar
  • For recent representative examples of ligandless Suzuki-Miyaura reactions catalyzed by heterogeneous catalyst on a solid support, see:
  • 12a Kudo D. Masui Y. Onaka M. Chem. Lett.  2007,  36:  918 
    Google Scholar
  • 12b Kazmaier U. Hähn S. Weiss TD. Kautenburger R. Maier WF. Synlett  2007,  2579 
    Google Scholar
  • 12c Artok L. Bulut H. Tetrahedron Lett.  2004,  45:  3881 
    Google Scholar
  • 12d Daku KML. Newton RF. Pearce SP. Vileb J. William JMJ. Tetrahedron Lett.  2003,  44:  5095 
    Google Scholar
13

Coating of Pd-SILC with PET as PET-Pd-SILC (4S): A Pd-SILC (108 mg, 0.027 mmol) silica gel pellet (5 mm in diameter and 5 mm in length) was immersed in a sat. solution of polyethylene terephthalate (60 mg) in 1,1,1,3,3,3-hexafluoro-2-propanol (0.1 mL). After removing the pellet from the solution with tweezers, the pellet was dried overnight in air under ambient conditions. The same procedure was repeated to give PET-Pd-SILC (4S; 123 mg).

14

The Suzuki-Miyaura reaction catalyzed by PET-Pd-SILC (4S); synthesis of 4-(2-methyl)phenylacetophenone: K2CO3 (149 mg, 1.08 mmol) and a pellet of PET-Pd-SILC (4S; 123 mg, 0.027 mmol) were added to a solution of 4-bromo-acetophenone (1; 107 mg, 0.54 mmol) and 2-methyl-phenylboronic acid (2; 103 mg, 0.76 mmol) in 50% aq EtOH (2 mL) under nitrogen. The solution was stirred at r.t. for 90 min. After decantation of the organic layer, the SILC pellet was rinsed with an Et2O-EtOH (1:1) mixture. The combined organic layers were evaporated to dryness under reduced pressure. Purification of the residue by column chromatog-raphy (EtOAc-n-hexane, 1:3) provided 4-(2-methyl)-phenylacetophenone (3; 115 mg, 100%).