Download PDF
Synlett 2011(9): 1324-1330  
DOI: 10.1055/s-0030-1260554
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of Functionalized 2-Arylthiophenes with Triarylbismuths as Atom-Efficient Multicoupling Organometallic Nucleophiles under Palladium Catalysis

Maddali L. N. Rao*, Debasis Banerjee, Ritesh J. Dhanorkar
Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur 208016, India
Fax: +91(512)2597532; e-Mail: maddali@iitk.ac.in;
Further Information

Publication History

Received 19 January 2011
Publication Date:
05 May 2011 (online)

    Permissions and Reprints All articles of this category

Abstract

Atom-efficient cross-coupling reactions of functionalized 2-bromo- and 2-iodothiophenes have been demonstrated using triarylbismuths as atom-efficient multicoupling organometallic nucleophiles under palladium-catalyzed conditions. These couplings with various functionalized triarylbismuths proceeded smoothly to afford the corresponding functionalized 2-arylthiophenes in high yields.

Key words

2-halothiophenes - cross-coupling - palladium catalysis - triarylbismuths - atom-efficient - multicoupling

    References and Notes

  • 1a Nicolaou KC. Bulger PG. Sarlah D. Angew. Chem. Int. Ed.  2005,  44:  4442 
    Google Scholar
  • 1b Hassan J. Sevignon M. Gozzi C. Schulz E. Lemaire M. Chem. Rev.  2002,  102:  1359 
    Google Scholar
  • 1c Kotha S. Lahiri K. Kashinath D. Tetrahedron  2002,  58:  9633 
    Google Scholar
  • 2a Schröter S. Stock C. Bach T. Tetrahedron  2005,  61:  2245 
    Google Scholar
  • 2b Handy CJ. Manoso AS. McElroy WT. Seganish WM. DeShong P. Tetrahedron  2005,  61:  12201 
    Google Scholar
  • 2c Guram AS. King AO. Allen JG. Wang X. Schenkel LB. Chan J. Bunel EE. Faul MM. Larsen RD. Martinelli MJ. Reider PJ. Org. Lett.  2006,  8:  1787 
    Google Scholar
  • 2d Guram AS. Wang X. Bunel EE. Faul MM. Larsen RD. Martinelli MJ. J. Org. Chem.  2007,  72:  5104 
    Google Scholar
  • 3a Babudri F. Farinola GM. Naso F. Synlett  2009,  2740 
    Google Scholar
  • 3b Koenen J.-M. Bilge A. Allard S. Alle R. Meerholz K. Scherf U. Org. Lett.  2009,  11:  2149 
    Google Scholar
  • 3c Collis GE. Burrell AK. Blandford EJ. Officer DL. Tetrahedron  2007,  63:  11141 
    Google Scholar
  • 3d Wang H. Wang J.-L. Yuan S.-C. Pei J. Pei W.-W. Tetrahedron  2005,  61:  8465 
    Google Scholar
  • 3e Arsenyan P. Pudova O. Popelis J. Lukevics E. Tetrahedron Lett.  2004,  45:  3109 
    Google Scholar
  • 3f Zrig S. Koeckelberghs G. Verbiest T. Andrioletti B. Rose E. Persoons A. Asselberghs I. Clays K. J. Org. Chem.  2007,  72:  5855 
    Google Scholar
  • 3g Letizia JA. Facchetti A. Stern CL. Ratner MA. Marks TJ. J. Am. Chem. Soc.  2005,  127:  13476 
    Google Scholar
  • 3h Nurkkala LJ. Steen RO. Friberg HKJ. Häggström JA. Bernhardt PV. Riley MJ. Dunne SJ. Eur. J. Inorg. Chem.  2008,  4101 
    Google Scholar
  • 4 Noguchi T. Hasegawa M. Tomisawa K. Mitsukuchi M. Bioorg. Med. Chem.  2003,  11:  4729 
    CrossrefGoogle Scholar
  • 5a Chandra R. Kung M.-P. Kung HF. Bioorg. Med. Chem. Lett.  2006,  16:  1350 
    Google Scholar
  • 5b Parai MK. Panda G. Chaturvedi V. Manju YK. Sinha S. Bioorg. Med. Chem. Lett.  2008,  18:  289 
    Google Scholar
  • 5c Wang W.-L. Chai SC. Ye Q.-Z. Bioorg. Med. Chem. Lett.  2009,  19:  1080 
    Google Scholar
  • 5d Wan Z.-K. Lee J. Xu W. Erbe DV. Joseph-McCarthy D. Follows BC. Zhang Y.-L. Bioorg. Med. Chem. Lett.  2006,  16:  4941 
    Google Scholar
  • 6a Kotha S. Kashinath D. Lahiri K. Sunoj RB. Eur. J. Org. Chem.  2004,  4003 
    Google Scholar
  • 6b Kotha S. Chakraborty K. Brahmachary E. Synlett  1999,  1621 
    Google Scholar
  • 6c Hassan J. Lavenot L. Gozzi C. Lemaire M. Tetrahedron Lett.  1999,  40:  857 
    Google Scholar
  • 6d Korolev DN. Bumagin NA. Tetrahedron Lett.  2005,  46:  5751 
    Google Scholar
  • 6e Martín-Santamaría S. Rodríguez J.-J. de Pascual-Teresa S. Gordon S. Bengtsson M. Garrido-Laguna I. Rubio-Viqueira B. López-Casas PP. Hidalgo M. de Pascual-Teresa B. Ramos A. Org. Biomol. Chem.  2008,  6:  3486 
    Google Scholar
  • 6f Costa SPG. Batista RMF. Cardoso P. Belsley M. Raposo MMM. Eur. J. Org. Chem.  2006,  3938 
    Google Scholar
  • 6g Pouchain L. Alévêque O. Nicolas Y. Oger A. Le Régent C.-H. Allain M. Blanchard P. Roncali J. J. Org. Chem.  2009,  74:  1054 
    Google Scholar
  • 6h Melucci M. Barbarella G. Sotgiu G. J. Org. Chem.  2002,  67:  8877 
    Google Scholar
  • 6i Lee K. Lee PH. Tetrahedron Lett.  2008,  49:  4302 
    Google Scholar
  • 6j Kondolff I. Doucet H. Santeli M. Synlett  2005,  2057 
    Google Scholar
  • 6k Molander GA. Biolatto B. J. Org. Chem.  2003,  68:  4302 
    Google Scholar
  • 6l Kotha S. Ghosh AK. Deodhar KD. Synthesis  2004,  549 
    Google Scholar
  • 6m Wong K.-T. Wang C.-F. Chou CH. Su YO. Lee G.-H. Peng S.-M. Org. Lett.  2002,  4:  4439 
    Google Scholar
  • 7a Silva NO. Abreu AS. Ferreira PMT. Monteiro LS. Queiroz M.-JRP. Eur. J. Org. Chem.  2002,  2524 
    Google Scholar
  • 7b Kneisel FF. Leuser H. Knochel P. Synthesis  2005,  2625 
    Google Scholar
  • 7c Fleckenstein CA. Plenio H. J. Org. Chem.  2008,  73:  3236 
    Google Scholar
  • 8a Toguem S.-MT. Villinger A. Langer P. Synlett  2009,  3311 
    Google Scholar
  • 8b Hussain M. Malik I. Villinger A. Langer P. Synlett  2009,  2691 
    Google Scholar
  • 8c Tuan DT. Tung DT. Langer P. Synlett  2006,  2812 
    Google Scholar
  • 8d Toguem S.-MT. Villinger A. Langer P. Synlett  2010,  909 
    Google Scholar
  • 8e Toguem S.-MT. Hussain M. Malik I. Villinger A. Langer P. Tetrahedron Lett.  2009,  50:  4962 
    Google Scholar
  • 8f Dang TT. Rasool N. Dang TT. Reinke H. Langer P. Tetrahedron Lett.  2007,  48:  845 
    Google Scholar
  • 8g Tùng DT. Tuan DT. Rasool N. Villinger A. Reinke H. Fischer C. Langer P. Adv. Synth. Catal.  2009,  351:  1595 
    Google Scholar
  • 9a Rao MLN. Banerjee D. Dhanorkar RJ. Synfacts  2010,  928 
    Google Scholar
  • 9b Rao MLN. Venkatesh V. Banerjee D. Synfacts  2008,  406 
    Google Scholar
  • 10a Rao MLN. Banerjee D. Dhanorkar RJ. Tetrahedron  2010,  66:  3623 
    Google Scholar
  • 10b Rao MLN. Jadhav DN. Dasgupta P. Org. Lett.  2010,  12:  2048 
    Google Scholar
  • 10c Rao MLN. Venkatesh V. Jadhav DN. Eur. J. Org. Chem.  2010,  3945 
    Google Scholar
  • 10d Rao MLN. Jadhav DN. Venkatesh V. Eur. J. Org. Chem.  2009,  4300 
    Google Scholar
  • 10e Rao MLN. Banerjee D. Giri S. J. Organomet. Chem.  2010,  695:  1518 
    Google Scholar
  • 10f Rao MLN. Banerjee D. Giri S. Tetrahedron Lett.  2009,  50:  5757 
    Google Scholar
  • 10g Rao MLN. Jadhav DN. Venkatesh V. Tetrahedron Lett.  2009,  50:  4268 
    Google Scholar
  • 10h Rao MLN. Jadhav DN. Banerjee D. Tetrahedron  2008,  64:  5762 
    Google Scholar
  • 10i Rao MLN. Venkatesh V. Jadhav DN.
    J. Organomet. Chem.  2008,  693:  2494 
    Google Scholar
  • 10j Rao MLN. Venkatesh V. Banerjee D. Tetrahedron  2007,  63:  12917 
    Google Scholar
  • 10k Rao MLN. Banerjee D. Jadhav DN. Tetrahedron Lett.  2007,  48:  6644 
    Google Scholar
  • 10l Rao MLN. Banerjee D. Jadhav DN. Tetrahedron Lett.  2007,  48:  2707 
    Google Scholar
  • 10m Rao MLN. Venkatesh V. Jadhav DN. Tetrahedron Lett.  2006,  47:  6975 
    Google Scholar
  • 11a Briand GG. Burford N. Chem. Rev.  1999,  99:  2601 
    Google Scholar
  • 11b Organobismuth Chemistry   Suzuki H. Matano Y. Elsevier; Amsterdam: 2001. 
    Google Scholar
  • 12 Green Chemistry: Theory and Practice   Anastas PT. Warner JC. Oxford University Press; USA: 2000. 
    Google Scholar
  • 13a Barton DHR. Ozbalik N. Ramesh M. Tetrahedron  1988,  44:  5661 
    Google Scholar
  • 13b Ohe T. Tanaka T. Kuroda M. Cho CS. Ohe K. Uemura S. Bull. Chem. Soc. Jpn.  1999,  72:  1851 
    Google Scholar
  • 15 Herbivo C. Comel A. Kirsch G. Raposo MMM. Tetrahedron  2009,  65:  2079 
    CrossrefGoogle Scholar
  • 16a Romagnoli R. Baraldi PG. Carrion MD. Cara CL. Cruz-Lopez O. Preti D. Tolomeo M. Grimaudo S. Cristina AD. Zonta N. Balzarini J. Brancale A. Sarkar T. Hamel E. Bioorg. Med. Chem.  2008,  16:  5367 
    Google Scholar
  • 16b Park JG. Sill PC. Makiyi EF. Garcia-Sosa AT. Millard CB. Schmidt JJ. Pang Y.-P. Bioorg. Med. Chem.  2006,  14:  395 
    Google Scholar
  • 17 Antonioletti R. D’Auria M. D’Onofrio F. Piancatelli G. Scettri A. J. Chem. Soc., Perkin Trans. 1  1986,  1755 
    CrossrefGoogle Scholar
14

Representative Procedure: An oven-dried Schlenk tube under a nitrogen atmosphere was charged with 2-bromo-thiophene (0.875 mmol, 3.5 equiv, 0.143 g) followed by BiPh3 (0.25 mmol, 1 equiv, 0.110 g), K3PO4 (1.5 mmol, 6 equiv, 0.318 g), Ph3P (0.10 mmol, 0.4 equiv, 0.026 g), Pd(OAc)2 (0.025 mmol, 0.1 equiv, 0.0056 g) and anhyd DMF (3 mL). The reaction mixture was stirred in an oil-bath at 90 ˚C for 1 h. The contents were cooled to r.t., quenched with H2O (10 mL) and extracted with EtOAc (2 × 20 mL). The combined organic extracts were washed with H2O, brine, dried (MgSO4) and concentrated under reduced pressure. The crude product was purified by column chromatography using 100-200 silica gel and petroleum ether as eluent to obtain 2-phenylthiophene as a white, low melting solid (0.097 g, 81%; isolated yield based on three aryl coupling from triphenylbismuth).