R. S. Roy, A. M. Gehring, J. C. Milne, P. J. Belshaw, and C. T. Walsh, Thiazole and oxazole peptides: biosynthesis and molecular machinery, Natural Product Reports, vol.16, issue.2, p.249, 1999.
DOI : 10.1039/a806930a

E. Aguilar and A. I. Meyers, Total synthesis of (???)-bistatramide C, Tetrahedron Letters, vol.35, issue.16, p.2477, 1994.
DOI : 10.1016/S0040-4039(00)77148-6

T. Martin, Thèse de doctorat de Chimie Organique de l'INSA de Rouen, mars, 2010.

T. E. Smith and E. P. Balskus, Synthetic Studies toward Hennoxazole A. Use of a Selective Bisoxazole Alkylation as the Key Fragment Coupling, HETEROCYCLES, vol.57, issue.7, p.1219, 2002.
DOI : 10.3987/COM-02-9480

E. H. Blackburn, C. W. Greider, W. Jack, E. H. Blackburn, C. W. Greider et al., Szostak prix Nobel de médecine, J. Pure & Appl. Chem. J. Org. Chem. J. Nat. Prod. Rep, vol.12, issue.25, p.227, 1133.

P. A. Jacobi and K. Lee, Total Synthesis of (??)-Stemoamide, Journal of the American Chemical Society, vol.119, issue.14, p.3409, 1997.
DOI : 10.1021/ja9642727

P. Wipf and C. P. Miller, A new synthesis of highly functionalized oxazoles, The Journal of Organic Chemistry, vol.58, issue.14, p.3604, 1993.
DOI : 10.1021/jo00066a004

D. R. Williams, D. A. Brooks, and M. A. Berliner, Total Synthesis of (???)-Hennoxazole A, Journal of the American Chemical Society, vol.121, issue.20, p.4924, 1999.
DOI : 10.1021/ja9904686

P. Liu, J. S. Panek, and F. Gerhart, Total Synthesis of (???)-Mycalolide A, Journal of the American Chemical Society, vol.122, issue.6, pp.1235-1277, 1968.
DOI : 10.1021/ja994003r

P. Janvier, X. Sun, H. Bienaymé, and J. Zhu, ]pyridin-5-one, Journal of the American Chemical Society, vol.124, issue.11, p.2560, 2002.
DOI : 10.1021/ja017563a

F. Zheng, H. Lin, Z. Zhan, A. R. Katritzky, R. Taylor et al., Advances in Heterocyclic Chemistry: Electrophilic Substitution of Heterocycles Quantitative Aspects, 53 Pan, pp.3148-54, 1990.

V. L. Rusinov, O. N. Chupakhin, G. G. Aleksandrov, B. König, V. N. Charushin et al., Heterocycles from transition metal catalysisc) Clayden, J. Organolithiums: Selectivity for Synthesis, Tetrahedron Lett. Tetrahedron Tetrahedron Chem. Rev. Tetrahedron Organic Chemistry Tetrahedron Chem. Soc. Rev. N, vol.47, issue.23, pp.1335-56, 1983.

K. Kitagawa and A. Inoue, 64 Exemples d'utilisation de magnésiates: (a)

R. E. Mulvey, F. Mongin, M. Uchiyama, Y. Kondo, Y. Fujiwara et al., (a) Moritani, I, Angew. Chem. Int. Ed. Tetrahedron Lett, vol.46, issue.12, p.68, 1119.

A. E. Shilov, G. B. Shul-'pin, R. H. Crabtree, A. R. Dick, M. S. Sanford et al., Dalton Trans, Chem. Rev. J. Chem. Soc. Tetrahedron J. Am. Chem. Soc. Jia, C. Pure Appl. Chem, vol.82, issue.91, pp.81-7166, 1969.

B. Mekonnen and G. Crank, Friedel-crafts reactions of 2-amino-4-(alkyl or aryl)oxazoles with acid chlorides and acid anhydrides: Synthesis of 5-acyl-2-amino-4-alkyloxazoles, Journal of Heterocyclic Chemistry, vol.29, issue.2, p.567, 1997.
DOI : 10.1002/jhet.5570340237

T. Yoshizumi, T. Satoh, K. Hirano, D. Matsuo, A. Orita et al., Synthesis of 2,5-diaryloxazoles through van Leusen reaction and copper-mediated direct arylation, Tetrahedron Letters, vol.50, issue.26, p.3273, 2009.
DOI : 10.1016/j.tetlet.2009.02.039

V. G. Zaitsev and O. Daugulis, Catalytic Coupling of Haloolefins with Anilides, Journal of the American Chemical Society, vol.127, issue.12, p.4156, 2005.
DOI : 10.1021/ja050366h

A. C. Giddens, H. I. Boshoff, S. G. Franzblau, C. E. Barry, and B. R. Copp, Antimycobacterial natural products: synthesis and preliminary biological evaluation of the oxazole-containing alkaloid texaline, Tetrahedron Letters, vol.46, issue.43, p.7355, 2005.
DOI : 10.1016/j.tetlet.2005.08.119

B. Valeur, Molecular fluorescence: principles and application, 2001.
DOI : 10.1002/9783527650002

O. Dreuille, P. Maszelin, H. Foehrenbach, G. Bonardel, J. F. Gaillard et al., Radiodiagnostic -Principes et techniques d'imagerie, 35-310-A-10, Encycl. Méd. Chir. Biochem. J. Kása, I.; Safrany, Á. Radiat. Phys. Chem, vol.22, issue.209 281, pp.76-1395, 1983.

B. 180-chah, L. Zikovsky, S. J. Culliford, P. Mccauley, A. Sutherland et al., Revue des sciences de l'eau, J, vol.3, issue.181, 1990.

J. Min, J. W. Lee, Y. Ahn, and Y. Chang, Combinatorial Dapoxyl Dye Library and its Application to Site Selective Probe for Human Serum Albumin, Journal of Combinatorial Chemistry, vol.9, issue.6, p.1079, 2007.
DOI : 10.1021/cc0700546

F. A. 192-zhuralev, Unprecedentedly mild direct Pd-catalyzed arylation of oxazolo[4,5-b]pyridine, Tetrahedron Letters, vol.47, issue.17, p.2929, 2006.
DOI : 10.1016/j.tetlet.2006.02.117

L. Campeau, M. Parisien, M. Leblanc, and K. Fagnou, Biaryl Synthesis via Direct Arylation:?? Establishment of an Efficient Catalyst for Intramolecular Processes, Journal of the American Chemical Society, vol.126, issue.30, p.9186, 2004.
DOI : 10.1021/ja049017y

. Anal, Calcd for C 13 H 11 NO 4 (245.2): C, 63.67; H, 4.52; N, 5.71. Found: C, 63.64; H, 4.39, pp.5-67

. Anal, Calcd for C 12 H 10 N 2 O 5 (262.2): C, 54.97; H, 3.84; N, 10.68. Found: C, 54, pp.3-76

. Anal, Calcd for C 13 H 13 NO 4 (247.2): C, 63.15; H, 5.30; N, 5.67. Found: C, 63.05; H, 4.97

. Hz, 34 (s, 1H)

. Anal, Calcd for C 10 H 9 NO 3 S (223.2): C, 53.80; H, 4.06

. Anal, Calcd for C 15 H 12 N 2 0 3 (268.3): C, 67.16; H, 4.51; N, 10.44. Found: C, 69.16; H, 4.19, pp.10-29

. Anal, Calcd for C 11 H 9 ClN 2 O 3 (252.7): C, 52.29; H, 3.59; Cl, 14.03

. Anal, Calcd for C 13 H 12 ClNO 4 (281.7): C, 55.43; H, 4.29; Cl, 12.59, pp.55-81

. Anal, Calcd for C 13 H 12 ClNO 4 (281.7): C, 55.43; H, 4.29; Cl, 12.59, pp.55-91

. Anal, Calcd for C 23 H 23 N 3 O 7 (453.4): C, 60.92; H, 5.11, pp.9-53

. Anal, Calcd for C 14 H 13 NO 4 (259.3): C, 64

. Anal, Calcd for C 20 H 19 NO 5 (353.4): C, 67.98; H, 5.42

. Anal, Calcd for C 16 H 13 NO 3 S (299.3): C, 64.20; H, 4.38, pp.64-79

. Anal, Calcd for C 14 H 19 NO 3 (249.3): C, 67.45

. Anal, Calcd for C 13 H 17 NO 3 (235.3): C, 66.36

. Anal, Calcd for C 16 H 17 NO 5 (303.3): C, 63.36; H, 5.65

. Hz, s, 1H, p.13

. Anal, Calcd for C 13 H 13 NO 3 (231.2): C, 67.52; H, 5.67; N, 6.06. Found: C, 67.72; H, 5.55, pp.5-97

. Hz, 06 (s, 1H)

. Anal, Calcd for C 17 H 15 NO 3 (281.3): C, 72.58; H, 5.37; N, 4.98. Found: C, 72.51; H, 5.22

. Anal, Calcd for C 13 H 12 FNO 3 (249.2): C, 62.65; H, 4.85; F, 7.62; N, 5.62. Found: C, 62.59; H, 4.67; F, 7.58, pp.1-4

. Anal, Calcd for C 9 H 11 NO 3 (181.2): C, 59.66; H, 6.12

. Acoet, PE 4:6, Rf = 0.35) afforded 52 (41%) as a white oil

. Hz, 09 (s, 1H)

C. Nmr, CDCl 3 , 75 MHz) ? = 13

. Anal, Calcd for C 7 H 9 NO 3 (155.1): C, 54.19; H, 5.85; N, 9.03. Found: C, 54.08; H, 5.78, pp.5-58

. Hz, 69 (s, 1H), 9.32 (s, 1H)

. Anal, Calcd for C 13 H 13 NO 4 (247.2): C, 63.15; H, 5.30; N, 5.67. Found: C, 62.84; H, 5, p.61

. Mmol, Standard workup followed by flash chromatography (EtOAc/PE 4/6, Rf = 0.29) afforded 69 (75%) as a white solid

. Anal, Calcd for C 21 H 19 N 3 O 3 (361.4): C, 69.79; H, 5.30; N, 11.63. Found: C, 69.99, pp.5-13

. Anal, Calcd for C 19 H 19 N 3 O 3 (337.4): C, 67.64; H, 5.68

=. Rf, 35) afforded 76 (92%) as a yellow solid (mp = 191-192 °C)

. Anal, Calcd for C 21 H 19 N 3 O 3 (361.4): C, 69.79; H, 5.30; N, 11.63. Found: C, 69, pp.5-26

. Anal, Calcd for C 19 H 19 N 3 O 3 (337.4): C, 67.64; H, 5.68; N, 12.46. Found: C, 67.84, pp.5-77

. Anal, Calcd for C 18 H 14 ClNO 3 (327.8): C, 65.96; H, 4.31; Cl, 10.82, pp.65-71

. Anal, Calcd for C 19 H 16 ClNO 4 (357.8): C, 63.78; H, 4.51; Cl, 9.91, p.6380

. Anal, Calcd for C 20 H 19 ClN 2 O 3 (370.8): C, 64.78; H, 5.16; Cl, 9.56, pp.64-93

. Anal, Calcd for C 19 H 13 ClN 2 O 3 (352.8): C, 64.69; H, 3.71; Cl, 10.05

. Anal, ): C, 68.74; H, 4.89; N, 9.72. Found: C, 68.63; H, 5.02

I. Chapitre, Mechanistic study of direct arylation reaction in oxazole-4- carboxylate serie Ethyl 5-methyloxazole-4-carboxylate 92

. Hz, 69 (s, 1H)

. Anal, Calcd for C 7 H 9 NO 3 (155.2): C, 54

. Anal, Calcd for C 19 H 17 NO 4 (323.3): C, 70.58; H, 5.30

. Anal, Calcd for C 19 H 17 NO 4 (323.3): C, 70.58; H, 5.30

. Anal, ): C, 71.69; H, 4.43

J. Roger, C. Verrier, R. Le-goff, C. Hoarau, and H. Doucet, Carbonates: Ecofriendly Solvents for Palladium-Catalyzed Direct 2-Arylation of Oxazole Derivatives, ChemSusChem, vol.73, issue.10, pp.951-956, 2009.
DOI : 10.1002/cssc.200900148
URL : https://hal.archives-ouvertes.fr/hal-00992145

C. Verrier, C. Hoarau, and F. Marsais, Direct palladium-catalyzed alkenylation, benzylation and alkylation of ethyl oxazole-4-carboxylate with alkenyl-, benzyl- and alkyl halides, Organic & Biomolecular Chemistry, vol.71, issue.4, pp.647-650, 2009.
DOI : 10.1039/b816374j

C. Verrier, T. Martin, C. Hoarau, and F. Marsais, Palladium-Catalyzed Direct (Hetero)arylation of Ethyl Oxazole-4-carboxylate: An Efficient Access to (Hetero)aryloxazoles, The Journal of Organic Chemistry, vol.73, issue.18, pp.7383-7386, 2008.
DOI : 10.1021/jo801093n

T. Martin, C. Verrier, C. Hoarau, and F. Marsais, Direct C-2 Arylation of Alkyl 4-Thiazolecarboxylates: New Insights in Synthesis of Heterocyclic Core of Thiopeptide Antibiotics, Organic Letters, vol.10, issue.13, pp.2909-2912, 2008.
DOI : 10.1021/ol801035c

N. Robert, C. Verrier, C. Hoarau, S. Célanire, and F. Marsais, A Convenient Synthesis of Cyclopenta[b]pyridin-2,5-dione as a Non-Glycosidic Cardiotonic Agent, ARKIVOC, p.92, 2008.

C. Verrier, C. Hoarau, and F. Marsais, Direct Regioselective Palladium-Catalyzed Arylation, Alkenylation, Benzylation and Alkylation of Ethyl Oxazole-4-Carboxylate with Halide Derivatives " 10 th, Tetrahedron Symposium Juillet, pp.23-26, 2009.

C. Verrier, C. Hoarau, and F. Marsais, Direct Regioselective C-H Bond Functionalization of Ethyl Oxazole-4-Carboxylate with Halide Derivatives, Journées Nord-Ouest Européenne Jeunes Chercheurs, pp.18-20, 2009.

C. Verrier, C. Hoarau, and F. Marsais, Novel Versatile Routes Towards Substituted Oxazoles Through Direct C-H Regioselective Palladium-Catalyzed Arylation, Vinylation and Alkylation of Ethyl 4-Oxazolecarboxylate" 11 th Belgium Organic Synthesis Symposium, BOSS XI) Juillet, pp.13-18, 2008.

C. Verrier, C. Hoarau, and F. Marsais, Etude de Nouvelles Voies de Fonctionnalisation en Série Oxazolique par Activation Directe de la Liaison C-H pour la Synthèse de Produits Naturels, Journées Nord-Ouest Européenne Jeunes Chercheurs, pp.9-10, 2008.

C. Verrier, C. Hoarau, and F. Marsais, Novel Versatile Routes Towards Substituted Oxazoles Through Direct C-H Regioselective Palladium-Catalyzed Arylation, Vinylation and Alkylation of Ethyl 4-Oxazolecarboxylate" 9 th Anglo-Norman Organic Chemistry Colloquium (ANORCQ), pp.3-5, 2008.

C. Verrier, C. Hoarau, and F. Marsais, Arylation et Hétéroarylation Régiosélective du 4- Oxazolecarboxylate d'Ethyle par Activation Directe de la Liaison C-H" Journées de Chimie Organique, Ecole Polytechnique, pp.17-19, 2007.

C. Hoarau, C. Verrier, P. Grandclaudon, A. Couture, and F. Marsais, Direct C-H Heteroarylation of Ethyl-4-Oxazolecarboxylate: Toward Natural Product Synthesis" 8 th Anglo-Norman Organic Chemistry Colloquium (ANORCQ), pp.9-11, 2006.

. Dr, Christophe Hoarau Directeur de thèse IRCOF Rue Tesnière 76130 Mont Saint Aignan christophe.hoarau@insa-rouen

. Pr, Francis Marsais Directeur de thèse IRCOF Rue Tesnière 76130 Mont Saint Aignan francis.marsais@insa-rouen

Y. Fujiwara, J. Chengguo, G. Dyker, A. Shilov, G. Shul-'pin et al., ) Examples of C-2 or C-5 regioselective direct (hetero)arylations of oxazole: (a) Derridj, (b) Nandurkar, N. S.; Bhanushali, M. Y.; Bhor, M. D, pp.1731-1770, 1997.

F. Mahuteau-betzer, D. S. Gierson, and S. Piguel, Examples of C-2 or C-5 direct (hetero)arylations of 5-or 2-monosub- stituted oxazoles: (a) Besselière, J. Org. Chem. P, vol.73, issue.3, pp.3278-3280, 2008.

C. Hz and . Nmr, 3100 cm -1 . Anal. Calcd for C 13 H 10 N 2 O 3 (242.2): C, 64.46; H, 4.16; N, 11.56. Found: C, 64.63; H, 4.10; N, 11.54. The characterization data of compounds 2c-j and others detailed C-2 direct arylating procedures are available in Supporting Informa- tion. General Procedure for C-5 Direct Coupling of 2-Aryl Oxazole-4-Carboxylate 2a (2b,f,g,j) with (Hetero)aryl Iodides and Bromides. To a 10-mL sealed tube were added oxazolecarboxylate 2a (76 mg, 0.35 mmol), (hetero)aryl bromide (0.35 mmol, Pd(OAc) The resulting mixture was stirred under N 2 at 110 °C. After filtration through Celite and concentration under vacuo, the crude product was purified by flash column chromatography on silica gel using a mixture of ethyl acetate/petrolum ether as the eluent to get, pp.22325-22328, 1551.

. Hz, 10 (d, 2H, J ) 8.6 Hz), 8.23 (d, 2H, J ) 8.1 Hz), pp.2994-2995, 1507.

. Anal, ): C, 68.96; H, 4.63; N, 8.04. Found: C, 69.06; H, 4.85; N, 8.21. The characterization data of compounds 3c-f and 5-8 and other C-5 direct arylating procedures are available in Supporting Informa- tion

K. J. Hodgett, M. T. Kershaw, . Org, and B. Lett-copp, For balsoxin and texaline synthesis via a combined cross-coupling or condensation and direct arylation approach, see: (a) (b) References 3a and 3b. (9) For the unique texaline synthesis via a condensation approach, see: (a) Gildens, A, JO801093N, vol.4, issue.8, pp.2905-2907, 2002.

E. Oi, Y. Aizawa, . G. Oginof-)-v, O. Zaitsev, . C. Daugulisb-)-d et al., For reviews, see: (a) This journal is, J. Org. Chem. J. Am. Chem. Soc. Tetrahedron In Heterocylic Compounds, vol.70, issue.60, p.3113, 2004.

S. Adachi, H. Matsuda, A. Kasai, Y. Takatsuki, O. Shizuri et al., 5 For a novel versatile preparation of 2-vinylated oxazole-4-carboxylates through cross-coupling metathesis reaction of 2-vinyl oxazole-4- caboxylate, see: T, Chem. Commun. J. Org. Chem. Tetrahedron Lett. Verrier, T. Matin, C. Hoarau and F. Marsais, J. Org. Chem. Org. Lett, vol.73, issue.46 8573, pp.73-7383, 1508.

G. Organ, M. Abdel-hadi, S. Avola, N. Hadei, J. Nasielski et al., HBP and PEPPSI-IPr catalysts have been successfully used for the challenging direct coupling of 1 with 2-(triisopropylsilyl)-4-iodooxazole, Chem. Eur. J. Angew. Chem., Int. Ed. Org. Lett, vol.13, issue.150 8, pp.10-2717, 1995.

H. Nmr, E. S. Gorelsky, D. Lapointe, K. Fagnoub, ). X. Wang et al., 11 For careful mechanism studies of palladium-catalyzed direct C?H functionalization of heteroaromatics with aryl halides, see: (a), J. Am. Chem. Soc. Org. Lett. J. Am. Chem. Soc. Tetrahedron Lett, vol.130, pp.129-5824, 2006.