Download PDF
Synlett 2013; 24(2): 254-258
DOI: 10.1055/s-0032-1317963
letter
© Georg Thieme Verlag Stuttgart · New York

The [RPPh3]2[Pd2X6] as a Catalyst Precursor for the Heck Cross-Coupling Reaction by in situ Formation of Stabilized Pd(0) Nanoparticles

Abdol Reza Hajipour*
a   Department of Pharmacology, University of Wisconsin Medical School, 1300 University Avenue, Madison, WI 53706-1532, USA
b   Pharmaceutical Research Laboratory, College of Chemistry, Isfahan University of Technology, Isfahan 84156, Iran   Fax: +98(311)3912350   Email: haji@cc.iut.ac.ir
,
Ghobad Azizi
b   Pharmaceutical Research Laboratory, College of Chemistry, Isfahan University of Technology, Isfahan 84156, Iran   Fax: +98(311)3912350   Email: haji@cc.iut.ac.ir
› Author Affiliations
Further Information

Publication History

Received: 10 November 2012

Accepted after revision: 10 December 2012

Publication Date:
08 January 2013 (online)

   Permissions and Reprints All articles of this category


Abstract

Pd(II) anionic, square planar complexes of the type [RPPh3]2[Pd2X2Cl4], where X = Cl, Br, have been applied for the first time as a catalyst precursor for the Heck reaction carried out in DMF at 140 °C. The highest yield was obtained for the most reducible ones, [MePPh3]2[Pd2Br2Cl4], in DMF in the presence of NaHCO3 as a base. It was found that during the reaction, phosphonium halide stabilized Pd(0) nanoparticles of about 10 nm, which have been formed in situ from the palladium(II) precursor and Pd(0) colloidal nanoparticles acts as the reservoir for Pd(II) species via activation of the metal surface through the oxidative addition of aryl halides.

Key words

olefination - arylation - catalysis - palladium - nano­structures

Supporting Information

    for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
  • Supporting Information
 

  • References and Notes

  • 1 Littke AF, Fu GC. J. Am. Chem. Soc. 2001; 123: 6989
    CrossrefPubMedSearch in Google Scholar
  • 2 Consorti CS, Flores FR, Dupont J. J. Am. Chem. Soc. 2005; 127: 12054
    CrossrefSearch in Google Scholar
  • 3 Schils D, Stappers F, Solberghe G, van Heck R, Coppens M, Van den Heuvel D, Van der Donck P, Callewaert T, Meeussen F, Bie ED, Eersels K, Schouteden E. Org. Process Res. Dev. 2008; 12: 530
    CrossrefSearch in Google Scholar
  • 4 Bouquillon S, du Moulinet d’Hardemare A, Averbuch-Pouchot M.-T, Hénin F, Muzart J. Polyhedron 1999; 18: 3511
    CrossrefSearch in Google Scholar
  • 5 Dullius JE. L, Suarez PA. Z, Einloft S, de Souza RF, Dupont J, Fischer J, De Cian A. Organometallics 1998; 17: 815
    CrossrefSearch in Google Scholar
  • 6 Zawartka W, Gniewek A, Trzeciaka AM, Ziłkowski JJ, Pernak J. J. Mol. Catal. A: Chem. 2009; 304: 8
    CrossrefSearch in Google Scholar
  • 7 Zawartka W, Trzeciak AM, Ziłkowski JJ, Lis T, Ciunik Z, Pernak J. Adv. Synth. Catal. 2006; 348: 1689
    CrossrefSearch in Google Scholar
  • 8 Baig S, Richard B, Serp P, Mijoule l, Hussein K, Guihéry N, Barthelat J, Kalck P. Inorg. Chem. 2006; 45: 1935
    CrossrefSearch in Google Scholar
  • 9 Makitova DD, Krasochka ON, Atovmyan LO, Letuchii YA, Roshchupkina OS. Coord. Chem. (Engl. Transl.) 1987; 13: 928
    Search in Google Scholar
  • 10 Kaufmann DE, Nouroozian M, Henze H. Synlett 1996; 1091
    Thieme Connect
  • 11 Gerritsma DA, Robertson A, McNulty J, Capretta A. Tetrahedron Lett. 2004; 45: 7629
    CrossrefSearch in Google Scholar
  • 12 Bhattacharya S, Srivastava A, Sengupta S. Tetrahedron Lett. 2005; 46: 3557
    CrossrefSearch in Google Scholar
  • 13 Precht MH. G, Scholten JD, Dupont J. Molecules 2010; 15: 3441
    CrossrefSearch in Google Scholar
  • 14 Typical Procedure for the Heck Arylation of Aryl Halides with Methyl Acrylate: Palladium complex ([MePPh3]2[Pd2Br2Cl4]) (0.01 mmol), methyl acrylate (0.5 mmol), aryl halides (0.25 mmol), NaHCO3 (0.5 mmol) and DMF (1.5 mL) were added to a 5-mL round-bottomed flask equipped with an efficient condenser and stirred at 140 °C in an oil bath for the time specified in Table 3. The course of the reaction was monitored by periodically taking samples and analyzing them by means of GC analysis. After cooling of the reaction mixture to r.t., the aqueous solution was extracted with hexane, the organic phase was dried over MgSO4, and the solvent was then removed under vacuum. Column chromatography on silica gel afforded the desired product. The product was characterized by 1H NMR and IR.