Download PDF
Synlett 2008(12): 1777-1780  
DOI: 10.1055/s-2008-1078565
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Copper-Free Sonogashira Reaction Using Gold Nanoparticles Supported on Ce2O3, Nb2O5 and SiO2 under Microwave Irradiation

Rodrigo O. M. A. de Souzaa, Mariana S. Bittara, Laiza V. P. Mendesa, Carla Michele F. da Silvaa, Victor Teixeira da Silvab, O. A. C. Antunes*a
a Instituto de Química, CT Bl. A 641, Cidade Universitária, Rio de Janeiro, RJ 21941-909, Brazil
Fax: +55(21)25627559; e-Mail: octavio@iq.ufrj.br;
b NUCAT/PEQ/COPPE/UFRJ, CT Bl. G, Cidade Universitária, Rio de Janeiro, RJ 21941-909, Brazil
Further Information

Publication History

Received 1 February 2008
Publication Date:
02 July 2008 (online)

   Permissions and Reprints All articles of this category
Preview

Abstract

In the present communication we wish to report a copper-free Sonogashira reaction catalyzed by gold-supported catalysts under microwave irradiation. Aryl and alkyl acetylenes were used and good yields were obtained with short reaction times when DMF was used as solvent. Three different supported gold catalysts were used and Au/SiO2 gave the best result for both aryl and alkyl acetylenes.

Key words

Sonogashira reaction - gold nanoparticles - supported catalyst

    References and Notes

  • 1a Sonogashira K. Tohda Y. Hagihara N. Tetrahedron Lett.  1975,  16:  4467 
    Search in Google Scholar
  • 1b Hierso JC. Doucet H. Angew. Chem. Int. Ed.  2007,  46:  835 
    Search in Google Scholar
  • 2 Chinchilla R. Nájera C. Chem. Rev.  2007,  107:  874 
    Search in Google Scholar
  • 3a Haruta M. Cattech  2002,  6:  102 
    Search in Google Scholar
  • 3b Ishida T. Haruta M. Angew. Chem. Int. Ed.  2007,  46:  7154 
    Search in Google Scholar
  • 3c Haruta M. Nature (London)  2005,  437:  1098 
    Search in Google Scholar
  • 4a Hashmi ASK. Chem. Rev.  2007,  107:  3180 
    Search in Google Scholar
  • 4b Marion N. Nolan SP. Angew. Chem. Int. Ed.  2007,  46:  2750 
    Search in Google Scholar
  • 4c Bond GC. Louis C. Thompson DT. Catalysis by Gold   Imperial College Press; London: 2006. 
  • 4d Widenhoefer RA. Han X. Eur. J. Org. Chem.  2006,  4555 
  • 4e Hashmi ASK. Hutchings GJ. Angew. Chem. Int. Ed.  2006,  45:  7896 
    Search in Google Scholar
  • 4f Hashmi ASK. Angew. Chem. Int. Ed.  2005,  44:  6990 
    Search in Google Scholar
  • 4g Astruc D. Lu F. Aranzes JR. Angew. Chem. Int. Ed.  2004,  44:  7852 
    Search in Google Scholar
  • 4h Schrekker HS. Gelesky MA. Stracke MP. Schrekker CML. Machado G. Teixeira SR. Rubim JC. Dupont J. J. Colloid Interface Sci.  2007,  316:  189 
    Search in Google Scholar
  • 4i Schelwies M. Dempwolff AL. Rominger F. Helmchen G. Angew. Chem. Int. Ed.  2007,  46:  5598 
    Search in Google Scholar
  • 4j Hashmi ASK. Schäfer S. Wölfle M. Gil CD. Fischer P. Laguna A. Blanco MC. Gimeno MC. Angew. Chem. Int. Ed.  2007,  46:  6184 
    Search in Google Scholar
  • 4k Deng X. Baker TA. Friend CM. Angew. Chem. Int. Ed.  2006,  45:  7075 
    Search in Google Scholar
  • 4l Brouwer C. He C. Angew. Chem. Int. Ed.  2006,  45:  1744 
    Search in Google Scholar
  • 4m Han X. Widenhoefer RA. Angew. Chem. Int. Ed.  2006,  45:  1747 
    Search in Google Scholar
  • 4n Lemière G. Gandon V. Agenet N. Goddard P. de Kozak A. Aubert C. Fernsterbank L. Malacria M. Angew. Chem. Int. Ed.  2006,  45:  7559 
    Search in Google Scholar
  • 4o Manea F. Houillon FB. Pasquato L. Scrimin P. Angew. Chem. Int. Ed.  2004,  43:  6165 
    Search in Google Scholar
  • 4p Hasmi ASK. Schwarz L. Choi J.-H. Frost TM. Angew. Chem. Int. Ed.  2000,  39:  2285 
    Search in Google Scholar
  • 4q Teles JH. Brode S. Chabanas M. Angew. Chem. Int. Ed.  1998,  37:  1415 
    Search in Google Scholar
  • 5a Corma A. Gonzalez-Arellano C. Iglesias M. Perez-Ferreras S. Sanchez F. Synlett  2007,  1771 
  • 5b González-Arellano C. Abad A. Corma A. Garcia H. Iglesias M. Sánchez F. Angew. Chem. Int. Ed.  2007,  46:  1536 
    Search in Google Scholar
  • 5c González-Arellano C. Corma A. Iglesias M. Sánchez F. J. Catal.  2006,  238:  497 
    Search in Google Scholar
  • 5d Carrettin S. Guzman J. Corma A. Angew. Chem. Int. Ed.  2005,  44:  2242 
    Search in Google Scholar
  • 5e Carrettin S. Corma A. Iglesias M. Sánchez F. Appl. Catal. A: Gen.  2005,  291:  247 
    Search in Google Scholar
  • 6a Coelho AV. Souza ALF. Lima PG. Wardell JL. Antunes OAC. Appl. Organomet. Chem.  2008,  22:  39 
    Search in Google Scholar
  • 6b Coelho AV. Souza ALF. Lima PG. Wardell JL. Antunes OAC. Tetrahedron Lett.  2007,  48:  7671 
    Search in Google Scholar
  • 6c Senra JD. Malta LFB. Souza ALF. Medeiros ME. Aguiar LCS. Antunes OAC. Tetrahedron Lett.  2007,  48:  8153 
    Search in Google Scholar
  • 6d Oliveira BL. Antunes OAC. Lett. Org. Chem.  2007,  4:  13 
    Search in Google Scholar
  • 6e Estrada GOD. Souza ALF. Silva JFM. Antunes OAC. Catal. Commun.  2008,  9:  1734 
    Search in Google Scholar
  • 6f Souza ALF. Silva LC. Oliveira BL. Antunes OAC. Tetrahedron Lett.  2008,  49:  3895 
    Search in Google Scholar
  • 7a Andrews SP. Stepan AF. Tanaka H. Ley SV. Smith MD. Adv. Synth. Catal.  2005,  347:  647 
    Search in Google Scholar
  • 7b Ji Y. Jain S. Davis RJ. J. Phys. Chem. B  2005,  109:  17232 
    Search in Google Scholar
  • 7c Cassol CC. Umpierre AP. Machado G. Wolke SI. Dupont J. J. Am. Chem. Soc.  2005,  127:  3298 
    Search in Google Scholar
  • 7d Yu K. Sommer W. Richardson J. Weck M. Jones CW. Adv. Synth. Catal.  2005,  347:  161 
    Search in Google Scholar
  • 7e Weck M. Jones CW. Inorg. Chem.  2007,  46:  1865 
    Search in Google Scholar
  • 7f Alimardanov A. Schmieder-van de Vondervoort L. de Vries AHM. de Vries JG. Adv. Synth. Catal.  2004,  346:  1812 
    Search in Google Scholar
  • 8a Martins DL. Alvarez HM. Aguiar LCS. Antunes OAC. Lett. Org. Chem.  2007,  4:  253 
    Search in Google Scholar
  • 8b Alvarez HM. Malta LFB. Herbst MH. Horn A. Antunes OAC. Appl. Catal. A: Gen.  207,  326:  82 
    Search in Google Scholar
  • 8c Valdés RH. Aranda DAG. Alvarez HM. Antunes OAC. Lett. Org. Chem.  2007,  4:  35 
    Search in Google Scholar
  • 8d Pimentel LCF. Souza ALF. Fernández TL. Wardell JL. Antunes OAC. Tetrahedron Lett.  2007,  48:  831 
    Search in Google Scholar
  • 8e Alvarez HM. Barbosa DP. Fricks AT. Aranda DAG. Valdés RH. Antunes OAC. Org. Process Res. Dev.  2006,  10:  941 
    Search in Google Scholar
  • 9a Loupy A. Microwaves in Organic Synthesis   Vol. 1:  Wiley-VCH; Weinheim: 2006. 
    Search in Google Scholar
  • 9b Loupy A. Microwaves in Organic Synthesis   Vol. 2:  Wiley-VCH; Weinheim: 2006. 
    Search in Google Scholar
  • 9c Kappe CO. Stadler A. Microwaves in Organic and Medicinal Chemistry   Wiley-VCH; Weinheim: 2005. 
  • 9d Dallinger D. Kappe CO. Chem. Rev.  2007,  107:  2563 
    Search in Google Scholar
  • 9e Hosseini M. Stiasni N. Barbieri V. Kappe CO. J. Org. Chem.  2007,  72:  1417 
    Search in Google Scholar
  • 9f Kremsner JM. Stadler A. Kappe CO. Top. Curr. Chem.  2006,  266:  233 
    Search in Google Scholar
  • 9g Kappe CO. Larhed M. Angew. Chem. Int. Ed.  2005,  44:  7666 
    Search in Google Scholar
  • 9h Kappe CO. Angew. Chem. Int. Ed.  2004,  43:  6250 
    Search in Google Scholar
  • 9i Desai B. Kappe CO. Top. Curr. Chem.  2004,  242:  177 
    Search in Google Scholar
10

A mixture of the aryl halide (1.00 mmol), Au-supported catalyst (3 mol%), phenylacetylene or 1-octyne (1.00 mmol) and K2CO3 (138 mg, 1.00 mmol) was mixed in DMF (5.0 mL). Microwave-assisted syntheses were conducted with a CEM Discover focussed microwave oven (150 W). After the reaction, usual aqueous workup and column chromatograph-ic purification process on silica gel (hexanes-EtOAc, 9:1) were carried out. The spectroscopic data of compounds 3, 8, 9, 13, 14 and 15 are as follows.
Compound 3: ¹H NMR (300 MHz, CDCl3): δ = 7.45-7.50 (m, 4 H), 7.20-7.25 (m, 6 H).
Compound 8: ¹H NMR (300 MHz, CDCl3): δ = 8.10 (m, 2 H), 7.95 (m, 2 H), 7.49-7.53 (m, 2 H), 7.20-7.25 (m, 3 H).
Compound 9: ¹H NMR (300 MHz, CDCl3): δ = 7.51 (m, 2 H), 7.46 (m, 2 H), 7.18-7.23 (m, 3 H), 6.84 (m, 2 H), 3.80 (s, 3 H).
Compound 13: ¹H NMR (300 MHz, CDCl3): δ = 7.25 (m, 1 H), 7.13 (m, 4 H), 2.38 (m, 2 H), 1.40 (m, 8 H), 0.89 (m, 3 H).
Compound 14: ¹H NMR (300 MHz, CDCl3): δ = 8.10 (m, 2 H), 7.89 (m, 2 H), 2.35 (m, 2 H), 1.33 (m, 8 H), 0.85 (m, 3 H).
Compound 15: ¹H NMR (300 MHz, CDCl3): δ = 7.36 (m, 2 H), 6.79 (m, 2 H), 3.55 (s, 3 H), 2.40 (m, 2 H), 1.45 (m, 8 H), 1.11 (m, 3 H).
Commercial Nb2O5 (49 m²/g¹) and SiO2 (200 m²/g), kindly provided by CBMM and DEGUSA, were used as received. CeO2 (20m²/g) was obtained by calcination of Ce(III) nitrate hexahydrate (ACROS, 99.5%) at 800 ˚C/h in a conventional oven. Gold was incorporated into the supports using the deposition-precipitation method at a constant pH of 8 by addition of Na2CO3 and using a HAuCl4 (ACROS) solution as gold source. Characterization of the catalysts by small-angle X-ray scattering (SAXS) revealed gold particle sizes of 4.9, 5.9 and 4.2 nm for Nb2O5, CeO2 and SiO2 supports, respectively.