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

Rodrigo O. M. A. de Souza; Mariana S. Bittar; Laiza V. P. Mendes; Carla Michele F. da Silva; Victor Teixeira da Silva; O. A. C. Antunes

doi:10.1055/s-2008-1078565

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Synlett 2008(12): 1777-1780
DOI: 10.1055/s-2008-1078565

LETTER

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

Rodrigo O. M. A. de Souza^a, Mariana S. Bittar^a, Laiza V. P. Mendes^a, Carla Michele F. da Silva^a, Victor Teixeira da Silva^b, 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

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Publication History

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

Abstract
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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

Google Scholar
1b Hierso JC. Doucet H. Angew. Chem. Int. Ed. 2007, 46: 835

Google Scholar
2 Chinchilla R. Nájera C. Chem. Rev. 2007, 107: 874

Google Scholar
3a Haruta M. Cattech 2002, 6: 102

Google Scholar
3b Ishida T. Haruta M. Angew. Chem. Int. Ed. 2007, 46: 7154

Google Scholar
3c Haruta M. Nature (London) 2005, 437: 1098

Google Scholar
4a Hashmi ASK. Chem. Rev. 2007, 107: 3180

Google Scholar
4b Marion N. Nolan SP. Angew. Chem. Int. Ed. 2007, 46: 2750

Google Scholar
4c Bond GC. Louis C. Thompson DT. Catalysis by Gold Imperial College Press; London: 2006.

Google Scholar
4d Widenhoefer RA. Han X. Eur. J. Org. Chem. 2006, 4555

Google Scholar
4e Hashmi ASK. Hutchings GJ. Angew. Chem. Int. Ed. 2006, 45: 7896

Google Scholar
4f Hashmi ASK. Angew. Chem. Int. Ed. 2005, 44: 6990

Google Scholar
4g Astruc D. Lu F. Aranzes JR. Angew. Chem. Int. Ed. 2004, 44: 7852

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

Google Scholar
4i Schelwies M. Dempwolff AL. Rominger F. Helmchen G. Angew. Chem. Int. Ed. 2007, 46: 5598

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

Google Scholar
4k Deng X. Baker TA. Friend CM. Angew. Chem. Int. Ed. 2006, 45: 7075

Google Scholar
4l Brouwer C. He C. Angew. Chem. Int. Ed. 2006, 45: 1744

Google Scholar
4m Han X. Widenhoefer RA. Angew. Chem. Int. Ed. 2006, 45: 1747

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

Google Scholar
4o Manea F. Houillon FB. Pasquato L. Scrimin P. Angew. Chem. Int. Ed. 2004, 43: 6165

Google Scholar
4p Hasmi ASK. Schwarz L. Choi J.-H. Frost TM. Angew. Chem. Int. Ed. 2000, 39: 2285

Google Scholar
4q Teles JH. Brode S. Chabanas M. Angew. Chem. Int. Ed. 1998, 37: 1415

Google Scholar
5a Corma A. Gonzalez-Arellano C. Iglesias M. Perez-Ferreras S. Sanchez F. Synlett 2007, 1771

Google Scholar
5b González-Arellano C. Abad A. Corma A. Garcia H. Iglesias M. Sánchez F. Angew. Chem. Int. Ed. 2007, 46: 1536

Google Scholar
5c González-Arellano C. Corma A. Iglesias M. Sánchez F. J. Catal. 2006, 238: 497

Google Scholar
5d Carrettin S. Guzman J. Corma A. Angew. Chem. Int. Ed. 2005, 44: 2242

Google Scholar
5e Carrettin S. Corma A. Iglesias M. Sánchez F. Appl. Catal. A: Gen. 2005, 291: 247

Google Scholar
6a Coelho AV. Souza ALF. Lima PG. Wardell JL. Antunes OAC. Appl. Organomet. Chem. 2008, 22: 39

Google Scholar
6b Coelho AV. Souza ALF. Lima PG. Wardell JL. Antunes OAC. Tetrahedron Lett. 2007, 48: 7671

Google Scholar
6c Senra JD. Malta LFB. Souza ALF. Medeiros ME. Aguiar LCS. Antunes OAC. Tetrahedron Lett. 2007, 48: 8153

Google Scholar
6d Oliveira BL. Antunes OAC. Lett. Org. Chem. 2007, 4: 13

Google Scholar
6e Estrada GOD. Souza ALF. Silva JFM. Antunes OAC. Catal. Commun. 2008, 9: 1734

Google Scholar
6f Souza ALF. Silva LC. Oliveira BL. Antunes OAC. Tetrahedron Lett. 2008, 49: 3895

Google Scholar
7a Andrews SP. Stepan AF. Tanaka H. Ley SV. Smith MD. Adv. Synth. Catal. 2005, 347: 647

Google Scholar
7b Ji Y. Jain S. Davis RJ. J. Phys. Chem. B 2005, 109: 17232

Google Scholar
7c Cassol CC. Umpierre AP. Machado G. Wolke SI. Dupont J. J. Am. Chem. Soc. 2005, 127: 3298

Google Scholar
7d Yu K. Sommer W. Richardson J. Weck M. Jones CW. Adv. Synth. Catal. 2005, 347: 161

Google Scholar
7e Weck M. Jones CW. Inorg. Chem. 2007, 46: 1865

Google Scholar
7f Alimardanov A. Schmieder-van de Vondervoort L. de Vries AHM. de Vries JG. Adv. Synth. Catal. 2004, 346: 1812

Google Scholar
8a Martins DL. Alvarez HM. Aguiar LCS. Antunes OAC. Lett. Org. Chem. 2007, 4: 253

Google Scholar
8b Alvarez HM. Malta LFB. Herbst MH. Horn A. Antunes OAC. Appl. Catal. A: Gen. 207, 326: 82

Google Scholar
8c Valdés RH. Aranda DAG. Alvarez HM. Antunes OAC. Lett. Org. Chem. 2007, 4: 35

Google Scholar
8d Pimentel LCF. Souza ALF. Fernández TL. Wardell JL. Antunes OAC. Tetrahedron Lett. 2007, 48: 831

Google Scholar
8e Alvarez HM. Barbosa DP. Fricks AT. Aranda DAG. Valdés RH. Antunes OAC. Org. Process Res. Dev. 2006, 10: 941

Google Scholar
9a Loupy A. Microwaves in Organic Synthesis Vol. 1: Wiley-VCH; Weinheim: 2006.

Google Scholar
9b Loupy A. Microwaves in Organic Synthesis Vol. 2: Wiley-VCH; Weinheim: 2006.

Google Scholar
9c Kappe CO. Stadler A. Microwaves in Organic and Medicinal Chemistry Wiley-VCH; Weinheim: 2005.

Google Scholar
9d Dallinger D. Kappe CO. Chem. Rev. 2007, 107: 2563

Google Scholar
9e Hosseini M. Stiasni N. Barbieri V. Kappe CO. J. Org. Chem. 2007, 72: 1417

Google Scholar
9f Kremsner JM. Stadler A. Kappe CO. Top. Curr. Chem. 2006, 266: 233

Google Scholar
9g Kappe CO. Larhed M. Angew. Chem. Int. Ed. 2005, 44: 7666

Google Scholar
9h Kappe CO. Angew. Chem. Int. Ed. 2004, 43: 6250

Google Scholar
9i Desai B. Kappe CO. Top. Curr. Chem. 2004, 242: 177

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 m^²/g^¹) and SiO₂ (200 m^²/g), kindly provided by CBMM and DEGUSA, were used as received. CeO₂ (20m^²/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.