Romero Fructos-Vázquez, ManuelBesora, MaríaBraga, Ataualpa A. C.Díaz Requejo, María MarMaseras, FeliuPérez Romero, Pedro José2019-04-252019-04-252017Fructos, M. R., Besora, M., Braga, A. A. C., Díaz-Requejo, M. M., Maseras, F., & Pérez, P. J. (2017). Mechanistic Studies on Gold-Catalyzed Direct Arene C–H Bond Functionalization by Carbene Insertion: The Coinage-Metal Effect. Organometallics, 36(1), 172-179. https://doi.org/10.1021/acs.organomet.6b006040276-73331520-6041 (electrónico)http://hdl.handle.net/10272/16190The catalytic functionalization of the Csp 2-H bond of benzene by means of the insertion of the CHCO2Et group from ethyl diazoacetate (N2=CHCO2Et) has been studied with the series of coinage metal complexes IPrMCl (IPr = IPr = 1,3-bis(diisopropylphenyl)imidazol-2-ylidene) and NaBArF 4 (BArF 4 = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate). For Cu and Ag, these examples constitute the first of such metals toward this transformation, that also provides ethyl cyclohepta-2,4,6-trienecarboxylate as by-product from the so-called Buchner reaction. In the case of methyl-substituted benzenes, the reaction exclusively proceeds onto the aromatic ring, the Csp 3-H bond remaining unreacted. A significant coinage metal effect has been observed, since the gold catalyst favors the formation of the insertion product into Csp 2-H bond whereas copper and silver preferentially induce the formation of the cycloheptatriene derivative. Experimental studies and theoretical calculations have explained the observed selectivity in terms of the formation of a common Wheland intermediate, resembling an electrophilic aromatic substitution, from which the reaction pathway evolves into two separate routes to each product.engAtribución-NoComercial-SinDerivadas 3.0 Españahttp://creativecommons.org/licenses/by-nc-nd/3.0/es/CopperSilver and gold catalysisArene C-H bond functionalizationCarbene transferDiazo reagentsjournal article10.1021/acs.organomet.6b00604open access