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

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.

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

References and Notes

<A NAME="RD01911ST-1A">1a</A> Nicolaou KC. Bulger PG. Sarlah D. Angew. Chem. Int. Ed.  2005,  44:  4442 

<A NAME="RD01911ST-1B">1b</A> Hassan J. Sevignon M. Gozzi C. Schulz E. Lemaire M. Chem. Rev.  2002,  102:  1359 

<A NAME="RD01911ST-1C">1c</A> Kotha S. Lahiri K. Kashinath D. Tetrahedron  2002,  58:  9633 

<A NAME="RD01911ST-2A">2a</A> Schröter S. Stock C. Bach T. Tetrahedron  2005,  61:  2245 

<A NAME="RD01911ST-2B">2b</A> Handy CJ. Manoso AS. McElroy WT. Seganish WM. DeShong P. Tetrahedron  2005,  61:  12201 

<A NAME="RD01911ST-2C">2c</A> 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 

<A NAME="RD01911ST-2D">2d</A> Guram AS. Wang X. Bunel EE. Faul MM. Larsen RD. Martinelli MJ. J. Org. Chem.  2007,  72:  5104 

<A NAME="RD01911ST-3A">3a</A> Babudri F. Farinola GM. Naso F. Synlett  2009,  2740 

<A NAME="RD01911ST-3B">3b</A> Koenen J.-M. Bilge A. Allard S. Alle R. Meerholz K. Scherf U. Org. Lett.  2009,  11:  2149 

<A NAME="RD01911ST-3C">3c</A> Collis GE. Burrell AK. Blandford EJ. Officer DL. Tetrahedron  2007,  63:  11141 

<A NAME="RD01911ST-3D">3d</A> Wang H. Wang J.-L. Yuan S.-C. Pei J. Pei W.-W. Tetrahedron  2005,  61:  8465 

<A NAME="RD01911ST-3E">3e</A> Arsenyan P. Pudova O. Popelis J. Lukevics E. Tetrahedron Lett.  2004,  45:  3109 

<A NAME="RD01911ST-3F">3f</A> Zrig S. Koeckelberghs G. Verbiest T. Andrioletti B. Rose E. Persoons A. Asselberghs I. Clays K. J. Org. Chem.  2007,  72:  5855 

<A NAME="RD01911ST-3G">3g</A> Letizia JA. Facchetti A. Stern CL. Ratner MA. Marks TJ. J. Am. Chem. Soc.  2005,  127:  13476 

<A NAME="RD01911ST-3H">3h</A> Nurkkala LJ. Steen RO. Friberg HKJ. Häggström JA. Bernhardt PV. Riley MJ. Dunne SJ. Eur. J. Inorg. Chem.  2008,  4101 

<A NAME="RD01911ST-4">4</A> Noguchi T. Hasegawa M. Tomisawa K. Mitsukuchi M. Bioorg. Med. Chem.  2003,  11:  4729 

<A NAME="RD01911ST-5A">5a</A> Chandra R. Kung M.-P. Kung HF. Bioorg. Med. Chem. Lett.  2006,  16:  1350 

<A NAME="RD01911ST-5B">5b</A> Parai MK. Panda G. Chaturvedi V. Manju YK. Sinha S. Bioorg. Med. Chem. Lett.  2008,  18:  289 

<A NAME="RD01911ST-5C">5c</A> Wang W.-L. Chai SC. Ye Q.-Z. Bioorg. Med. Chem. Lett.  2009,  19:  1080 

<A NAME="RD01911ST-5D">5d</A> Wan Z.-K. Lee J. Xu W. Erbe DV. Joseph-McCarthy D. Follows BC. Zhang Y.-L. Bioorg. Med. Chem. Lett.  2006,  16:  4941 

<A NAME="RD01911ST-6A">6a</A> Kotha S. Kashinath D. Lahiri K. Sunoj RB. Eur. J. Org. Chem.  2004,  4003 

<A NAME="RD01911ST-6B">6b</A> Kotha S. Chakraborty K. Brahmachary E. Synlett  1999,  1621 

<A NAME="RD01911ST-6C">6c</A> Hassan J. Lavenot L. Gozzi C. Lemaire M. Tetrahedron Lett.  1999,  40:  857 

<A NAME="RD01911ST-6D">6d</A> Korolev DN. Bumagin NA. Tetrahedron Lett.  2005,  46:  5751 

<A NAME="RD01911ST-6E">6e</A> 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 

<A NAME="RD01911ST-6F">6f</A> Costa SPG. Batista RMF. Cardoso P. Belsley M. Raposo MMM. Eur. J. Org. Chem.  2006,  3938 

<A NAME="RD01911ST-6G">6g</A> Pouchain L. Alévêque O. Nicolas Y. Oger A. Le Régent C.-H. Allain M. Blanchard P. Roncali J. J. Org. Chem.  2009,  74:  1054 

<A NAME="RD01911ST-6H">6h</A> Melucci M. Barbarella G. Sotgiu G. J. Org. Chem.  2002,  67:  8877 

<A NAME="RD01911ST-6I">6i</A> Lee K. Lee PH. Tetrahedron Lett.  2008,  49:  4302 

<A NAME="RD01911ST-6J">6j</A> Kondolff I. Doucet H. Santeli M. Synlett  2005,  2057 

<A NAME="RD01911ST-6K">6k</A> Molander GA. Biolatto B. J. Org. Chem.  2003,  68:  4302 

<A NAME="RD01911ST-6L">6l</A> Kotha S. Ghosh AK. Deodhar KD. Synthesis  2004,  549 

<A NAME="RD01911ST-6M">6m</A> Wong K.-T. Wang C.-F. Chou CH. Su YO. Lee G.-H. Peng S.-M. Org. Lett.  2002,  4:  4439 

<A NAME="RD01911ST-7A">7a</A> Silva NO. Abreu AS. Ferreira PMT. Monteiro LS. Queiroz M.-JRP. Eur. J. Org. Chem.  2002,  2524 

<A NAME="RD01911ST-7B">7b</A> Kneisel FF. Leuser H. Knochel P. Synthesis  2005,  2625 

<A NAME="RD01911ST-7C">7c</A> Fleckenstein CA. Plenio H. J. Org. Chem.  2008,  73:  3236 

<A NAME="RD01911ST-8A">8a</A> Toguem S.-MT. Villinger A. Langer P. Synlett  2009,  3311 

<A NAME="RD01911ST-8B">8b</A> Hussain M. Malik I. Villinger A. Langer P. Synlett  2009,  2691 

<A NAME="RD01911ST-8C">8c</A> Tuan DT. Tung DT. Langer P. Synlett  2006,  2812 

<A NAME="RD01911ST-8D">8d</A> Toguem S.-MT. Villinger A. Langer P. Synlett  2010,  909 

<A NAME="RD01911ST-8E">8e</A> Toguem S.-MT. Hussain M. Malik I. Villinger A. Langer P. Tetrahedron Lett.  2009,  50:  4962 

<A NAME="RD01911ST-8F">8f</A> Dang TT. Rasool N. Dang TT. Reinke H. Langer P. Tetrahedron Lett.  2007,  48:  845 

<A NAME="RD01911ST-8G">8g</A> Tùng DT. Tuan DT. Rasool N. Villinger A. Reinke H. Fischer C. Langer P. Adv. Synth. Catal.  2009,  351:  1595 

<A NAME="RD01911ST-9A">9a</A> Rao MLN. Banerjee D. Dhanorkar RJ. Synfacts  2010,  928 

<A NAME="RD01911ST-9B">9b</A> Rao MLN. Venkatesh V. Banerjee D. Synfacts  2008,  406 

<A NAME="RD01911ST-10A">10a</A> Rao MLN. Banerjee D. Dhanorkar RJ. Tetrahedron  2010,  66:  3623 

<A NAME="RD01911ST-10B">10b</A> Rao MLN. Jadhav DN. Dasgupta P. Org. Lett.  2010,  12:  2048 

<A NAME="RD01911ST-10C">10c</A> Rao MLN. Venkatesh V. Jadhav DN. Eur. J. Org. Chem.  2010,  3945 

<A NAME="RD01911ST-10D">10d</A> Rao MLN. Jadhav DN. Venkatesh V. Eur. J. Org. Chem.  2009,  4300 

<A NAME="RD01911ST-10E">10e</A> Rao MLN. Banerjee D. Giri S. J. Organomet. Chem.  2010,  695:  1518 

<A NAME="RD01911ST-10F">10f</A> Rao MLN. Banerjee D. Giri S. Tetrahedron Lett.  2009,  50:  5757 

<A NAME="RD01911ST-10G">10g</A> Rao MLN. Jadhav DN. Venkatesh V. Tetrahedron Lett.  2009,  50:  4268 

<A NAME="RD01911ST-10H">10h</A> Rao MLN. Jadhav DN. Banerjee D. Tetrahedron  2008,  64:  5762 

<A NAME="RD01911ST-10I">10i</A> Rao MLN. Venkatesh V. Jadhav DN.
J. Organomet. Chem.  2008,  693:  2494 

<A NAME="RD01911ST-10J">10j</A> Rao MLN. Venkatesh V. Banerjee D. Tetrahedron  2007,  63:  12917 

<A NAME="RD01911ST-10K">10k</A> Rao MLN. Banerjee D. Jadhav DN. Tetrahedron Lett.  2007,  48:  6644 

<A NAME="RD01911ST-10L">10l</A> Rao MLN. Banerjee D. Jadhav DN. Tetrahedron Lett.  2007,  48:  2707 

<A NAME="RD01911ST-10M">10m</A> Rao MLN. Venkatesh V. Jadhav DN. Tetrahedron Lett.  2006,  47:  6975 

<A NAME="RD01911ST-11A">11a</A> Briand GG. Burford N. Chem. Rev.  1999,  99:  2601 

<A NAME="RD01911ST-11B">11b</A> Organobismuth Chemistry   Suzuki H. Matano Y. Elsevier; Amsterdam: 2001. 

<A NAME="RD01911ST-12">12</A> Green Chemistry: Theory and Practice   Anastas PT. Warner JC. Oxford University Press; USA: 2000. 

<A NAME="RD01911ST-13A">13a</A> Barton DHR. Ozbalik N. Ramesh M. Tetrahedron  1988,  44:  5661 

<A NAME="RD01911ST-13B">13b</A> Ohe T. Tanaka T. Kuroda M. Cho CS. Ohe K. Uemura S. Bull. Chem. Soc. Jpn.  1999,  72:  1851 

<A NAME="RD01911ST-14">14</A>

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).

<A NAME="RD01911ST-15">15</A> Herbivo C. Comel A. Kirsch G. Raposo MMM. Tetrahedron  2009,  65:  2079 

<A NAME="RD01911ST-16A">16a</A> 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 

<A NAME="RD01911ST-16B">16b</A> Park JG. Sill PC. Makiyi EF. Garcia-Sosa AT. Millard CB. Schmidt JJ. Pang Y.-P. Bioorg. Med. Chem.  2006,  14:  395 

<A NAME="RD01911ST-17">17</A> Antonioletti R. D’Auria M. D’Onofrio F. Piancatelli G. Scettri A. J. Chem. Soc., Perkin Trans. 1  1986,  1755