J. Hz, 20 (d, 1 H, J = 5.6 Hz, p.15

. Hz, 4.66 (d, 1 H, J = 5.6 Hz

. Ome, 36 (sept, 1 H, J = 6.9 Hz12 (s, 3 H

. Godula, D. Sames, J. Scienceb-)-yamaguchi, A. Yamaguchi, K. Itami et al., Organotransition Metal Chemistry: From Bonding to Catalysis (d) Negishi, E.-i.; de Meijere, A. Handbook of Organopalladium Chemistry for Organic Synthesis, c) Ackermann, L. Modern Arylation Methods, pp.67-8960, 2002.

L. Ackermann, S. J. Acs-catal-blanksby, and G. B. Ellison, (9) For selected examples of ruthenacycles of type I, see: (a) Li, Acc. Chem. Res. B, vol.36, issue.8, p.255, 2003.

K. Jing, H. Xu, and G. Wang, For other ruthenacyles, see: (i) Djukic, Chem. Eur. J. J. P.; Sortais, J.-B, vol.2017, issue.3285

L. Ackermann, R. Born, P. Alvarez-bercedo, and L. Ackermann, Ruthenium(IV) Alkylidenes as Precatalysts for Direct Arylations of Alkenes with Aryl Chlorides and an Application to Sequential Catalysis, Angewandte Chemie International Edition, vol.61, issue.33, p.6364, 2007.
DOI : 10.1016/j.tet.2005.09.095

D. Gelman, S. J. Garden, L. Ackermann, B. Stefane, H. B. Zugelj et al., Six- Membered Heterocycles: 1,2-, 1,3-, and 1,4-Diazines and Related Systems in Modern Heterocyclic Chemistry, Chem. Eur. J. Eur. J. Org. Chem, issue.11, 1248.

A. Bothara, K. G. Mini-rev, . Med, I. M. Chem-lagoja, K. Pieterse et al., (d) Mangalagiu I. I, Chem. Biodiv. Curr. Org. Chem. Chem. Eur. J. J. Am. Chem. Soc. J. Chem. Commun. N. Dyes Pigm, vol.13, issue.3075971, pp.1607-730, 1963.

S. Achelle, I. Nouira, B. Pfaffinger, Y. Ramondenc, N. Ple et al., V-Shaped 4,6-Bis(arylvinyl)pyrimidine Oligomers: Synthesis and Optical Properties, The Journal of Organic Chemistry, vol.74, issue.10, p.3711, 2009.
DOI : 10.1021/jo900107u

L. Pascal, Y. Van-haverbeke, P. Dubois, . Synth, F. Commun-pozgan et al., (6b) and 1583229 (8) contain the supplementary crystallographic daa for this article. These data can be obtained free of charge from The Cambridge Crsyta- llographic Data Centre (CCDC) at www) For C-H bond arylation on thiophene with a ruthenium catalyst , see, 21) For arylation mechanisms on heteroaromatic C-H bonds, pp.31-3167, 1315.

C. B. Bheeter, L. Chen, J. Soule, H. Doucet, . Cat et al., Organic Reactions (b) Lectka, T. Active Metal ? Preparation, Characterization, Applications; Fürstner , A, Synthesis Chem. Commun. Chem. Rev J. Top. Stereochem. C, vol.38, issue.2125, pp.1-223, 1979.

Y. Aihara, N. Chatani, and J. Diez, (26) For a structure similar to Ru-2, see: (a) Cadierno, Chem. Eur. J. 2013 Chem. Sci, vol.19, p.7595

J. Garcia-alvarez, J. Gimeno, R. Organometallics-regragui, P. H. Dixneuf, N. J. Taylor et al., For examples of ruthenium(p-cymene)-coordinated CO at ? >200 ppm in 13 C NMR spectroscopy, see: (b), p.1020, 1984.

Y. D. Smurnyy, M. Pink, K. G. Caulton, P. Am-kuzman, F. Pozgan et al., Stereochemistry of Organic Compounds (32) For a precedent of a transition metal-mediated chlorination of similar molecules with CuCl2, Chem. Soc. ChemCatChem Angew. Chem. Int. Ed. J. Top. Stereochem. Chem. Soc. Rev. Chem. Soc. Rev. C. Top. Organomet . Chem. Chem. Soc. Rev. Tetrahedron J. Chem. Res. Synop, vol.127, issue.64, pp.8944-8971, 1979.