Synthesis 2017; 49(20): 4676-4686
DOI: 10.1055/s-0036-1589071
special topic
© Georg Thieme Verlag Stuttgart · New York

Improved Synthesis of Symmetrical 2,5-Diarylimidazoles by One-Pot Palladium-Catalyzed Direct Arylation Tailored on the Electronic Features of the Aryl Halide

Marco Lessi
a  Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via G. Moruzzi 13, 56124 Pisa, Italy   Email: fabio.bellina@unipi.it
,
Gianmarco Panzetta
a  Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via G. Moruzzi 13, 56124 Pisa, Italy   Email: fabio.bellina@unipi.it
,
Giulia Marianetti
b  Scuola Normale Superiore, Piazza dei Cavalieri 7, 56126 Pisa, Italy
,
a  Dipartimento di Chimica e Chimica Industriale, Università di Pisa, Via G. Moruzzi 13, 56124 Pisa, Italy   Email: fabio.bellina@unipi.it
› Author Affiliations
This work was supported by the Università di Pisa under the projects PRA 2015 (project no. 2015_0038) and PRA 2017 (project no. 2017_28).
Further Information

Publication History

Received: 22 May 2017

Accepted after revision: 19 June 2017

Publication Date:
31 July 2017 (online)

Dedicated to Prof. Renzo Rossi on the occasion of his 80th birthday

Published as part of the Special Topic Modern Strategies for Heterocycles Synthesis

Abstract

Two methods for the one-pot synthesis of 2,5-diarylimidazoles by palladium-catalyzed direct C–H arylation of 1-substituted imidazoles with aryl bromides have been devised. The first method, promoted by copper(I) iodide, is best suited for electron-poor aryl bromides, and also allows the 2,5-diarylation of thiazole and oxazole. The use of xylene instead of DMA is the key for the efficiency of the second method, which gives the best results with electron-rich aryl bromides.

Supporting Information

 
  • References


    • For selected reviews on the biological activities of aryl-substituted imidazoles, see:
    • 1a Bellina F. Cauteruccio S. Rossi R. Tetrahedron 2007; 63: 4571
    • 1b Shalini K. Kumar Sharma P. Kumar N. Der Chimica Sinica 2010; 1 (03) : 36
    • 1c Zhang L. Peng X.-M. Damu GL. V. Geng R.-X. Zhou C.-H. Med. Res. Rev. 2014; 34: 340
    • 1d Rossi R. Lessi M. Manzini C. Marianetti G. Bellina F. Synthesis 2016; 48: 3821
    • 2a Fridman N. Speiser S. Kafrory M. Cryst. Growth Des. 2006; 6: 1653
    • 2b Kulkánek J. Burês F. Beilstein J. Org. Chem. 2012; 8: 25
    • 2c Liu H.-H. Chen Y. Tetrahedron 2013; 69: 1872
  • 3 Klikar M. Solanke P. Tydlitát J. Burês F. Chem. Rec. 2016; 16: 1886
    • 4a Krygowski TM. Szatylowicz H. Stasyuk OA. Dominikowska J. Palusiak M. Chem. Rev. 2014; 114: 6383
    • 4b Pandey SK. Manogaran D. Manogaran S. Schaefer HF. III. J. Phys. Chem. A 2016; 120: 2894
    • 5a Radziszewski B. Ber. Dtsch. Chem. Ges. 1877; 10: 70
    • 5b Yanover D. Kaftory M. Acta Crystallogr., Sect. E 2009; 65: o711
    • 6a Minei P. Battisti A. Barondi S. Lessi M. Bellina F. Ruggeri G. Pucci A. ACS Macro Lett. 2013; 2: 317
    • 6b Lessi M. Manzini C. Minei P. Perego LA. Bloino J. Egidi F. Barone V. Pucci A. Bellina F. ChemPlusChem 2014; 79: 366
    • 6c Barone V. Bellina F. Biczysko M. Bloino J. Fornaro T. Latouche C. Lessi M. Marianetti G. Minei P. Panattoni A. Pucci A. Phys. Chem. Chem. Phys. 2015; 17: 26710
    • 6d Bellina F. Manzini C. Marianetti G. Pezzetta C. Fanizza E. Lessi M. Minei P. Barone V. Pucci A. Dyes Pigm. 2016; 134: 118
  • 7 Bellina F. Manzini C. Lessi M. Eur. J. Org. Chem. 2013; 5621

    • For selected representative reviews on the direct C–H arylation of imidazoles, see:
    • 8a Satoh T. Miura M. Chem. Lett. 2007; 36: 200
    • 8b Alberico D. Scott ME. Lautens M. Chem. Rev. 2007; 107: 174
    • 8c Bellina F. Rossi R. Tetrahedron 2009; 65: 10269
    • 8d Roger J. Gottumukkala AL. Doucet H. ChemCatChem 2010; 2: 20
    • 8e Rossi R. Bellina F. Lessi M. Manzini C. Perego LA. Synthesis 2014; 46: 2833
    • 8f Rossi R. Lessi M. Manzini C. Marianetti G. Bellina F. Synthesis 2016; 48: 3821
    • 9a Aoyagi Y. Inoue A. Koizumi I. Hashimoto R. Tokunaga K. Gohma K. Komatsu J. Sekine K. Miyafuji A. Kunoh J. Homma R. Akita Y. Ohta A. Heterocycles 1992; 33: 257
    • 9b Pivsa-Art S. Satoh T. Kawamura Y. Miura M. Nomura M. Bull. Chem. Soc. Jpn. 1998; 71: 467
    • 9c Kondo Y. Komine T. Sakamoto T. Org. Lett. 2000; 2: 3111
    • 9d Bellina F. Cauteruccio S. Mannina L. Rossi R. Viel S. J. Org. Chem. 2005; 70: 3997
    • 9e Touré BB. Lane BS. Sames D. Org. Lett. 2006; 8: 1979
    • 9f Chiong HA. Daugulis O. Org. Lett. 2007; 9: 1449
    • 9g Bellina F. Cauteruccio S. Di Fiore A. Marchetti C. Rossi R. Tetrahedron 2008; 64: 6060
    • 9h Bellina F. Cauteruccio S. Di Fiore A. Rossi R. Eur. J. Org. Chem. 2008; 5436
    • 9i Roger J. Doucet H. Tetrahedron 2009; 65: 9772
    • 9j Joo JM. Touré BB. Sames D. J. Org. Chem. 2010; 75: 4911
    • 9k Kumar PV. Lin W.-S. Shen J.-S. Nandi D. Lee HM. Organometallics 2011; 30: 5160
    • 9l Shinahara F. Yamauchi T. Yamaguchi E. Murai T. J. Org. Chem. 2012; 77: 8815
    • 9m Skogh A. Fransson R. Sköld C. Larhed M. Sandström A. J. Org. Chem. 2013; 78: 12251
    • 9n He X.-X. Li Y. Ma B.-B. Ke Z. Liu F.-S. Organometallics 2016; 35: 2655
    • 10a Bellina F. Cauteruccio S. Mannina L. Rossi R. Viel S. Eur. J. Org. Chem. 2006; 693
    • 10b Bellina F. Cauteruccio S. Rossi R. Eur. J. Org. Chem. 2006; 1379
    • 10c Bellina F. Calandri C. Cauteruccio S. Rossi R. Tetrahedron 2007; 63: 1970
    • 10d Bellina F. Cauteruccio S. Rossi R. J. Org. Chem. 2007; 72: 8543
    • 10e Yamauchi T. Shibahara F. Murai T. J. Org. Chem. 2014; 79: 7185
    • 10f Bellina F. Guazzelli N. Lessi M. Manzini C. Tetrahedron 2015; 71: 2298
  • 11 Arai N. Takahashi M. Mitani M. Mori A. Synlett 2006; 3170
    • 12a Shibahara F. Yamaguchi E. Murai T. Chem. Commun. 2010; 46: 2471
    • 12b Shibahara F. Yamagichi E. Murai T. J. Org. Chem. 2011; 76: 2680
  • 13 Takfaoui A. Zhao L. Touzani R. Soulé J.-F. Dixneuf PH. Doucet H. Tetrahedron 2014; 70: 8316
  • 14 For an interesting study on acetate-assisted C–H activation at Pd(IV) centers, see: Maleckis A. Kampf JW. Sanford MS. J. Am. Chem. Soc. 2013; 135: 6618
    • 15a Gorelsky SI. Coord. Chem. Rev. 2013; 257: 153
    • 15b Perego LA. Grimaud L. Bellina F. Adv. Synth. Catal. 2016; 358: 597 ; and references cited therein
  • 16 Khake SM. Jagtap RA. Dangat YB. Gonnade RG. Vanka K. Punji B. Organometallics 2016; 35: 875