D. Popp and W. E. Mcewen, Polyphosphoric Acids As A Reagent In Organic Chemistry, Chemical Reviews, vol.58, issue.2, p.321, 1958.
DOI : 10.1021/cr50020a004

K. Horii, Y. Ninomiya, and . Tamura, Studies on Terramycin and Its Related Compounds. V, YAKUGAKU ZASSHI, vol.76, issue.2, p.163, 1956.
DOI : 10.1248/yakushi1947.76.2_163

R. L. Zhang, E. M. Hertzler, T. Holt, E. J. Vickstrom, J. Eisenbraum et al., Kirsch Synthesis, pp.735-735, 1993.

E. Migianu, G. Brault, E. Migianu, A. Néguesque, E. Battaglia et al., Kirsch Synthesis, Eur. J. Med. Chem, pp.40-757, 1096.

). I. Ferreira, M. R. Queiroz, and G. Kirsch, Novel synthetic routes to thienocarbazoles via palladium or copper catalyzed amination or amidation of arylhalides and intramolecular cyclization, Tetrahedron, vol.58, issue.39, pp.7943-59, 2002.
DOI : 10.1016/S0040-4020(02)00904-3

L. Joseph, G. Martarello, J. Kirsch, D. Chem, L. Joseph et al., Research (S) 1995, 448. (b), P. Nabet, B. Dousset J. Med. Chem, vol.43, issue.2, pp.367-410, 1996.

M. Fernandez, A. Castaño, E. Domingez, A. Escribano, D. Jiang et al., A novel class of AMPA receptor allosteric modulators. Part 1: Design, synthesis, and SAR of 3-aryl-4-cyano-5-substituted-heteroaryl-2-carboxylic acid derivatives, Bioorganic & Medicinal Chemistry Letters, vol.16, issue.19, p.5057, 2006.
DOI : 10.1016/j.bmcl.2006.07.035

T. Noda, H. Ogawa, N. Noma, Y. Shirota, T. Noda et al., -terthiophene, for organic electroluminescent devices, Applied Physics Letters, vol.280, issue.6, pp.699-239, 1997.
DOI : 10.1002/adma.19930051204

R. W. Sabnis and D. W. , Synthesis of azo benzo[b]thiophene derivatives and their application as disperse dyes, Dyes and Pigments, vol.10, issue.4, p.295, 1989.
DOI : 10.1016/0143-7208(89)85017-X

S. Hesse, E. Perspicace, and G. Kirsch, Microwave Assisted Synthesis of 2-Aminothiophene-3-carboxylic Derivatives, 3H-Thieno, Tetrahedron Lett, vol.22, 2007.

D. Thomae, G. Kirsch, and O. , Seck Synthesis, 1027.

M. Aadil and G. , Kirsch Phosphorus, Sulfur and Silicon, p.91, 1993.

K. Gewald and U. , Hain Organische Chemie Und Biochemie, p.455, 1992.

H. H. Hodgson, The Sandmeyer Reaction., Chemical Reviews, vol.40, issue.2, p.251, 1947.
DOI : 10.1021/cr60126a003

J. Tsuji, Palladium Reagents and Catalysts-Inovations in Organic Synthesis, pp.1-5

A. S. Guram, S. L. Buchwald, J. P. Wolfe, S. Wagaw, and S. L. Buchwald, Palladium-Catalyzed Aromatic Aminations with in situ Generated Aminostannanes, Journal of the American Chemical Society, vol.116, issue.17, pp.7901-7948, 1994.
DOI : 10.1021/ja00096a059

S. Shekhar, P. Ryberg, J. F. Hartwig, J. S. Mathew, D. G. Blackmond et al., Reevaluation of the Mechanism of the Amination of Aryl Halides Catalyzed by BINAP-Ligated Palladium Complexes, Journal of the American Chemical Society, vol.128, issue.11, pp.3584-366, 2002.
DOI : 10.1021/ja045533c

J. E. Lakshman, K. R. Ogawa, S. D. Radke, and S. Rothstein, Palladium-catalyzed C???N and C???C cross-couplings as versatile, new avenues for modifications of purine 2???-deoxynucleosides, Journal of Organometallic Chemistry, vol.653, issue.1-2, p.234, 2002.
DOI : 10.1016/S0022-328X(02)01267-6

A. S. Dallas and K. V. Gothelf, Effect of Water on the Palladium-Catalyzed Amidation of Aryl Bromides, The Journal of Organic Chemistry, vol.70, issue.8, p.3321, 2005.
DOI : 10.1021/jo0500176

W. Schäffer and B. , Selektive ??therspaltung von 4-Hydroxy-methoxy-chinolincarbons??ureestern, Chemische Berichte, vol.1953, issue.1, p.160, 1966.
DOI : 10.1002/cber.19660990127

F. D. Popp and W. E. Mcewen, Polyphosphoric Acids As A Reagent In Organic Chemistry, Chemical Reviews, vol.58, issue.2, p.321, 1958.
DOI : 10.1021/cr50020a004

J. Koo, Studies in Polyphosphoric Acid Cyclizations, Journal of the American Chemical Society, vol.75, issue.8, p.1891, 1953.
DOI : 10.1021/ja01104a034

Z. Horii, K. Ninomiya, and Y. , Studies on Terramycin and Its Related Compounds. V, YAKUGAKU ZASSHI, vol.76, issue.2, p.163, 1956.
DOI : 10.1248/yakushi1947.76.2_163

V. Premasagar, V. A. Palaniswamy, and E. J. Eisenbraum, Methanesulfonic acid catalyzed cyclization of 3-arylpropanoic and 4-arylbutanoic acids to 1-indanones and 1-tetralones, The Journal of Organic Chemistry, vol.46, issue.14, p.2974, 1981.
DOI : 10.1021/jo00327a028

J. Andre, J. Dormoy, A. Cativiela, A. Avenoza, M. Paris et al., Heymes Synthetic Comm, J. Org.Chem. J. Med. Chem, vol.59, issue.49, pp.7774-9257, 1992.

J. Whittaker, 1019. c) H, Chem. Soc. Wynberg J. Am. Chem. Soc, vol.80, p.364, 1956.

D. Pla, A. Marchal, C. A. Olsen, F. Albericio, and M. Álvarez, Modular Total Synthesis of Lamellarin D, The Journal of Organic Chemistry, vol.70, issue.20, p.8231, 2005.
DOI : 10.1021/jo051083a

H. Ihmels, K. Faulhaber, and G. Viola, Evaluation of the DNA-Binding Properties of Cationic Dyes by Absorption and Emission Spectroscopy, Highlights in Biorganic Chemistry : Methods and Applications, pp.172-187, 2004.
DOI : 10.1002/3527603727.ch2e

H. Zhang, Q. Cai, and D. Ma, Amino Acid Promoted CuI-Catalyzed C???N Bond Formation between Aryl Halides and Amines or N-Containing Heterocycles, The Journal of Organic Chemistry, vol.70, issue.13, p.5164, 2005.
DOI : 10.1021/jo0504464

A. Aziz, I. El-subbagh, and T. , Lewis acid-promoted transformation of 2-alkoxypyridines into 2-aminopyridines and their antibacterial activity. Part 2: Remarkably facile C???N bond formation, Bioorganic & Medicinal Chemistry, vol.13, issue.16, p.4929, 2005.
DOI : 10.1016/j.bmc.2005.05.027

). M. Manhas, S. G. Amin, M. S. Manhas, S. G. Amin, S. D. Sharma et al., Heterocydic compounds. VIII. Synthesis of 3- and 2,3-substituted thienopyrimidones, Journal of Heterocyclic Chemistry, vol.99, issue.1, pp.161-371, 1977.
DOI : 10.1002/jhet.5570140134

R. J. Ife, T. H. Brown, P. Blurton, D. J. Keeling, C. A. Leach et al., Reversible Inhibitors of the Gastric (H+/K+)-ATPase. 5. Substituted 2,4-Diaminoquinazolines and Thienopyrimidines, Journal of Medicinal Chemistry, vol.38, issue.14, p.2763, 1995.
DOI : 10.1021/jm00014a027

G. Sommen, A. Comel, and G. , Kirsch Synthesis Column chromatography (CH 2 Cl 2 /cyclohexane, 1:9 to 1:1) gave compound 3 as a purple solid (115 mg, 69 %), pp.7-10, 2003.

. Hz, 18 (s, 1 H, NH) ppm. 13 C NMR (63 MHz CDCl 3 ): ? = 22, 139.3 (CH)CO 2 Me) ppm. IR (KBr): ? ? = 3198 (NH), 1663 (C=O)

. Hz, 80 (s, 2 H, NH) ppm. 13 C NMR (63 MHz, CDCl 3 ): ? = 22, pp.24-29

. Hz, 37 (s, 1 H, NH) ppm. 13 C NMR (63 MHz CDCl 3 ): ? = 14, 130.7 (C), 139.5 (C), 141.2 (C) R) ppm. IR (KBr): ? ? = 2925 (NH), pp.1727-1659

J. =. Ethyl, Column chromatography (CH 2 Cl 2 /cyclohexane, 1:1 to 8:2) gave compound 11 as a yellow pale solid (148 mg CDCl 3 ): ? = 1.37 (t, J = 7.1 Hz, 3 H), 2.71 (s, 3 H, SCH 3, dd, J = 7.9 and 7.9 Hz, 1 H, ArH), 9.12 (s, 1 H, NH) ppm. 13 C NMR (63 MHz (C) ppm. IR (KBr): ? ? = 3288 (NH), pp.156-158, 1945.

A. Cyclohexane, S. Begouin, M. R. Hesse, and G. Queiroz, From thiophene 1c and 2,6- dibromopyridine column chromatography (CH 2 Cl 2 Kirsch FULL PAPER 3:2 to 3:1) gave compound 13 as a yellow pale solid (30 mg, 22 %) or from thiophene 1c and 2,6-diiodopyridine (CH 2 Cl 2 /cyclohexane, 1:1 to 3:1; 70 mg, 51 %), p.62

. Hz, 59 (s, 2 H, NH) ppm. 13 C NMR (63 MHz, CDCl 3 ): ? = 51, CH) 111.5 (2 CH) CH) C) ppm. IR (KBr), pp.3257-1670

. Hz, 77 (s, 1 H, NH) ppm. 13 C NMR (63 MHz CDCl 3 ): ? = 51, 123.7 (CH) 166.7 (C) ppm. IR (KBr): ? ? = 3225 (NH), pp.1670-1671

. Hz, 60 (s, 1 H, ArH), 9.87 (s, 1 H, NH) ppm. 13 C NMR (63 MHz, CDCl 3 ): ? = 14, m, 3 H, ArH), 7.64 (d, J = 8.3 Hz (C) ppm. IR (KBr): ? ? = 3293 (NH, pp.4-377037

J. =. Ethyl, Column chromatography (CH 2 Cl 2 /cyclohexane, 2:3 to 1:1) gave compound 16 as a yellow solid (71 mg, 32 %). M.p. 193? 195 °C. 1 H NMR (250 MHz, CDCl 3 ): ? = 1, ArH), 7.49 (dd, J = 8.0 and 8.0 Hz, 1 H, ArH), 8.34 (s, 2 H, ArH), 9.64 (s, 2 H, NH) ppm. 13 C NMR (63 MHz CH), pp.37-60

. Hz, 88 (s, 1 H, NH) ppm. 13 C NMR (63 MHz CDCl 3 ): ? = 14, CH) CH) (C) ppm. IR (KBr): ? ? = 3307 (NH), pp.60-165

H. , A. M. Hooper, M. Utsunomiya, J. F. Hartwig, and J. Org, Acknowledgments Financial support from the SRI of UPV-M is gratefully acknowledged . We also thank Egide (France) / Grices (Portugal) for support through the Pessoa program, 11.22 (s, 1 H, NH) ppm. 13 C NMR (63 MHz 123.1 (C), 127.8 (CH), 128.4 (CH)COCH 3 ) ppm. IR (KBr): ? ? = 3265 (NH), 1687 (C=O), 1662 (C=O) cm ?1 . C 23 H 22, pp.133-134, 2000.

M. P. Doyle, B. Siegfried, and J. F. Dellaria, Alkyl nitrite-metal halide deamination reactions. 2. Substitutive deamination of arylamines by alkyl nitrites and copper(II) halides. A direct and remarkably efficient conversion of arylamines to aryl halides, The Journal of Organic Chemistry, vol.42, issue.14, pp.2426-2430, 1977.
DOI : 10.1021/jo00434a017

J. F. Hartwig, Transition Metal Catalyzed Synthesis of Arylamines and Aryl Ethers from Aryl Halides and Triflates: Scope and Mechanism, Angewandte Chemie International Edition, vol.37, issue.15, pp.2046-2067, 1998.
DOI : 10.1002/(SICI)1521-3773(19980817)37:15<2046::AID-ANIE2046>3.0.CO;2-L

S. Wagaw and S. L. Buchwald, The Synthesis of Aminopyridines:?? A Method Employing Palladium-Catalyzed Carbon???Nitrogen Bond Formation, The Journal of Organic Chemistry, vol.61, issue.21, pp.7240-7241, 1996.
DOI : 10.1021/jo9612739

H. Wolfe, J. P. Tomori, J. Sadighi, S. L. Yin, and . Buchwald, Simple, Efficient Catalyst System for the Palladium-Catalyzed Amination of Aryl Chlorides, Bromides, and Triflates, The Journal of Organic Chemistry, vol.65, issue.4, pp.1158-1174, 2000.
DOI : 10.1021/jo991699y

T. H. Jonckers, B. U. Maes, G. L. Lemière, and R. Dommisse, Selective palladium-catalyzed aminations on dichloropyridines, Tetrahedron, vol.57, issue.32, pp.7027-7034, 2001.
DOI : 10.1016/S0040-4020(01)00659-7

A. Aziz, I. El-subbagh, and T. Kunieda, Lewis acid-promoted transformation of 2-alkoxypyridines into 2-aminopyridines and their antibacterial activity. Part 2: Remarkably facile C???N bond formation, Bioorganic & Medicinal Chemistry, vol.13, issue.16, pp.4929-4935, 2005.
DOI : 10.1016/j.bmc.2005.05.027

. Hartwig-est-une-méthode-efficace-de-synthèse-d-'arylamines, Jusqu'à présent, la synthèse d'arylamines en série thiophénique n'avait été que peu décrite. Nous nous sommes ainsi intéressés à la réactivité de dérivés substitués des 2-et 3-bromothiophènes dans les couplages C-N palladocatalysés. Par la suite