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Synthesis 2011(21): 3530-3546  
DOI: 10.1055/s-0030-1260213
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Palladium-Catalysed C2 or C5 Direct Arylation of 3-Substituted Thiophenes with Aryl Bromides

Jia Jia Dong, David Roy, Reny Jacob Roy, Marina Ionita, Henri Doucet*
Institut Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes ‘Catalyse et Organometalliques’, Campus de Beaulieu, 35042 Rennes, France
Fax: +33(2)23236939; e-Mail: henri.doucet@univ-rennes1.fr;
Further Information

Publication History

Received 1 July 2011
Publication Date:
07 September 2011 (online)

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Abstract

The Pd(OAc)2/dppb system was found to be an efficient catalyst for the direct arylation of 3-substituted thiophene derivatives. The regioselectivity of the arylation strongly depends on the thiophene substituent and also on the nature of the aryl bromide. When using 3-formyl, 3-cyano, 3-methyl, 3-hydroxymethyl or 3-bromothiophene, the 2-arylated thiophenes were obtained with 76-95% regioselectivity; whereas, the arylation of 3-formylthiophene diethylacetal or 3-acetylthiophene gave the 5-arylated thiophenes with 52-90% regioselectivity. The use of congested aryl bromides favours the arylation at C5. These reactions were performed using only 0.1 mol% of catalyst. Moreover, this procedure has been found to be tolerant to a variety of functional groups on the aryl bromide such as formyl, propionyl, benzoyl, nitrile, and nitro.

Key words

catalysis - palladium - thiophenes - arylation - C-H bond activation

    References

  • 1a Li JJ. Gribble GW. Palladium in Heterocyclic Chemistry   Pergamon; Amsterdam: 2000. 
    Google Scholar
  • 1b Handbook of Organopalladium Chemistry for Organic Synthesis   Negishi E. Wiley-Interscience; New York: 2002.  Part III. p.213 
    Google Scholar
  • 2 Ohta A. Akita Y. Ohkuwa T. Chiba M. Fukunaga R. Miyafuji A. Nakata T. Tani N. Aoyagi Y. Heterocycles  1990,  31:  1951 
    CrossrefGoogle Scholar
  • 3a Alberico D. Scott ME. Lautens M. Chem. Rev.  2007,  107:  174 
    Google Scholar
  • 3b Satoh T. Miura M. Chem. Lett.  2007,  36:  200 
    Google Scholar
  • 3c Campeau L.-C. Stuart DR. Fagnou K. Aldrichimica Acta  2007,  40:  35 
    Google Scholar
  • 3d Seregin IV. Gevorgyan V. Chem. Soc. Rev.  2007,  36:  1173 
    Google Scholar
  • 3e Li B.-J. Yang S.-D. Shi Z.-J. Synlett  2008,  949 
    Google Scholar
  • 3f Mori A. Sugie A. Bull. Chem. Soc. Jpn.  2008,  81:  548 
    Google Scholar
  • 3g McGlacken GP. Batman LM. Chem. Soc. Rev.  2009,  38:  2447 
    Google Scholar
  • 3h Ackermann L. Vincente R. Kapdi AR. Angew. Chem. Int. Ed.  2009,  48:  9792 
    Google Scholar
  • 3i Roger J. Gottumukkala AL. Doucet H. ChemCatChem  2010,  2:  20 
    Google Scholar
  • 3j Fischmeister C. Doucet H. Green Chem.  2011,  13:  741 
    Google Scholar
  • For recent examples of palladium-catalysed direct arylation or vinylation of heteroaromatics with aryl halides from our laboratory, see:
  • 4a Gottumukkala AL. Doucet H. Adv. Synth. Catal.  2008,  350:  2183 
    Google Scholar
  • 4b Gottumukkala AL. Derridj F. Djebbar S. Doucet H. Tetrahedron Lett.  2008,  49:  2926 
    Google Scholar
  • 4c Fall Y. Doucet H. Santelli M. ChemSusChem  2009,  2:  153 
    Google Scholar
  • 4d Roger J. Doucet H. Adv. Synth. Catal.  2009,  351:  1977 
    Google Scholar
  • 4e Fall Y. Reynaud C. Doucet H. Santelli M. Eur. J. Org. Chem.  2009,  4041 
    Google Scholar
  • 4f Dong JJ. Roger J. Pozgan F. Doucet H. Green Chem.  2009,  11:  1832 
    Google Scholar
  • 4g Derridj F. Gottumukkala AL. Djebbar S. Doucet H. Eur. J. Inorg. Chem.  2008,  2550 
    Google Scholar
  • 4h Roger J. Doucet H. Tetrahedron  2009,  65:  9772 
    Google Scholar
  • 4i Roger J. Verrier C. Le Goff R. Hoarau C. Doucet H. ChemSusChem  2009,  2:  951 
    Google Scholar
  • 4j Ionita M. Roger J. Doucet H. ChemSusChem  2010,  3:  367 
    Google Scholar
  • 4k Fall Y. Doucet H. Santelli M. Synthesis  2010,  127 
    Google Scholar
  • For selected examples of palladium-catalysed direct arylations of thiophenes, see:
  • 5a Penalva V. Lavenot L. Gozzi C. Lemaire M. Appl. Catal., A  1999,  182:  399 
    Google Scholar
  • 5b Okazawa T. Satoh T. Miura M. Nomura M. J. Am. Chem. Soc.  2002,  124:  5286 
    Google Scholar
  • 5c Masui K. Ikegami H. Mori A. J. Am. Chem. Soc.  2004,  126:  5074 
    Google Scholar
  • 5d Masui K. Mori A. Okano K. Takamura K. Kinoshita M. Ikeda T. Org. Lett.  2004,  6:  2011 
    Google Scholar
  • 5e Yokooji A. Satoh T. Miura M. Nomura M. Tetrahedron  2004,  60:  6757 
    Google Scholar
  • 5f Mitsudo K. Thansandote P. Wilhelm T. Mariampillai B. Lautens M. Org. Lett.  2006,  8:  3939 
    Google Scholar
  • 5g Mashraqui SH. Ashraf M. Ghadigaonkar SG. Synlett  2006,  2423 
    Google Scholar
  • 5h Amaladass P. Clement JA. Mohanakrishnan AK. Tetrahedron  2007,  63:  10363 
    Google Scholar
  • 5i Turner GL. Morris JA. Greaney MF. Angew. Chem. Int. Ed.  2007,  46:  7996 
    Google Scholar
  • 5j David E. Pellet-Rostaing S. Lemaire M. Tetrahedron  2007,  63:  8999 
    Google Scholar
  • 5k Arai N. Miyaoku T. Teruya S. Mori A. Tetrahedron Lett.  2008,  49:  1000 
    Google Scholar
  • 5l Derridj F. Roger J. Geneste F. Djebbar S. Doucet H. J. Organomet. Chem.  2009,  694:  455 
    Google Scholar
  • 5m Smaliy RV. Beauperin M. Cattey H. Meunier P. Hierso J.-C. Roger J. Doucet H. Coppel Y. Organometallics  2009,  28:  3152 
    Google Scholar
  • 5n Liégault B. Lapointe D. Caron L. Vlassova A. Fagnou K. J. Org. Chem.  2009,  74:  1826 
    Google Scholar
  • 5o Roger J. Pozgan F. Doucet H. Green Chem.  2009,  11:  425 
    Google Scholar
  • 5p Dong JJ. Roger J. Doucet H. Tetrahedron Lett.  2009,  50:  2778 
    Google Scholar
  • 5q Dong JJ. Roger J. Verrier C. Martin T. Le Goff R. Hoarau C. Doucet H. Green Chem.  2010,  12:  2053 
    Google Scholar
  • 5r Derridj F. Roger J. Djebbar S. Doucet H. Org. Lett.  2010,  12:  4320 
    Google Scholar
  • 5s Laidaoui N. Miloudi A. El Abed D. Doucet H. Synthesis  2010,  2553 
    Google Scholar
  • 5t Beydoun K. Doucet H.
    J. Organomet. Chem.  2011,  696:  1749 
    Google Scholar
  • 5u Roy D. Mom S. Beaupérin M. Doucet H. Hierso J.-C. Angew. Chem. Int. Ed.  2010,  49:  6650 
    Google Scholar
  • 6 For examples of palladium-catalysed intramolecular direct 2-arylations of 3-substituted thiophenes, see: Mori A. Arai N. Hatta T. Monguchi D. Heterocycles  2010,  80:  103 
    CrossrefGoogle Scholar
  • For examples of palladium-catalysed direct polyarylations of 3-substituted thiophenes, see:
  • 7a Nakano M. Tsurugi H. Satoh T. Miura M. Org. Lett.  2008,  10:  1851 
    Google Scholar
  • 7b Shibahara F. Yamaguchi E. Murai T. Chem. Commun.  2010,  2471 
    Google Scholar
  • 8 Glover B. Harvey KA. Liu B. Sharp MJ. Tymoschenko MF. Org. Lett.  2003,  5:  301 
    CrossrefPubMedGoogle Scholar
  • 9 Lavenot L. Gozzi C. Ilg K. Orlova I. Penalva V. Lemaire M. J. Organomet. Chem.  1998,  567:  49 
    CrossrefGoogle Scholar
  • 10 Fournier dit Chabert J. Marquez B. Neville L. Joucla L. Broussous S. Bouhours P. David E. Pellet-Rostaing S. Marquet B. Moreau N. Lemaire M. Bioorg. Med. Chem.  2007,  15:  4482 
    CrossrefGoogle Scholar
  • 11 Forgione P. Brochu M.-C. St-Onge M. Thesen KH. Bailey MD. Bilodeau F. J. Am. Chem. Soc.  2006,  128:  11350 
    CrossrefPubMedGoogle Scholar
  • 12 Liégault B. Petrov I. Gorlesky SI. Fagnou K. J. Org. Chem.  2010,  75:  1047 
    CrossrefGoogle Scholar
  • 13 Borghese A. Geldhof G. Antoine L. Tetrahedron Lett.  2006,  47:  9249 
    CrossrefGoogle Scholar
  • 14 Rene O. Fagnou K. Org. Lett.  2010,  9:  2116 
    Google Scholar
  • 15 Yanagisawa S. Ueda K. Sekizawa H. Itami K. J. Am. Chem. Soc.  2009,  131:  14622 
    CrossrefGoogle Scholar
  • 16 Yanagisawa S. Sudo T. Noyori R. Itami K. Tetrahedron  2008,  64:  6073 
    CrossrefGoogle Scholar
  • 17 Dong JJ. Doucet H. Eur. J. Org. Chem.  2010,  611 
    Google Scholar
  • 18 Roger J. Pozgan F. Doucet H. Adv. Synth. Catal.  2010,  352:  696 
    CrossrefGoogle Scholar
  • 19 Barluenga J. Trincado M. Rubio E. Gonzalez JM. Angew. Chem. Int. Ed.  2006,  45:  3140 
    CrossrefPubMedGoogle Scholar
  • 20 Roth GP. Farina V. Tetrahedron Lett.  1995,  36:  2191 
    CrossrefGoogle Scholar
  • 21 Denton TT. Zhang X. Cashman JR. J. Med. Chem.  2005,  48:  224 
    CrossrefGoogle Scholar