RT Journal Article
T1 Mechanistic Studies on Gold-Catalyzed Direct Arene C–H Bond Functionalization by Carbene Insertion: The Coinage-Metal Effect
A1 Romero Fructos-Vázquez, Manuel
A1 Besora, María
A1 Braga, Ataualpa A. C.
A1 Díaz Requejo, María Mar
A1 Maseras, Feliu
A1 Pérez Romero, Pedro José
AB The catalytic functionalization of the Csp2-H bond of benzene by means of the insertion of the CHCO2Etgroup 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 NaBArF4 (BArF4 = 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 ethylcyclohepta-2,4,6-trienecarboxylate as by-product from the so-called Buchner reaction. In the case of methyl-substitutedbenzenes, the reaction exclusively proceeds onto the aromatic ring, the Csp3-H bond remaining unreacted. A significantcoinage metal effect has been observed, since the gold catalyst favors the formation of the insertion product into Csp2-Hbond whereas copper and silver preferentially induce the formation of the cycloheptatriene derivative. Experimental studiesand theoretical calculations have explained the observed selectivity in terms of the formation of a common Whelandintermediate, resembling an electrophilic aromatic substitution, from which the reaction pathway evolves into two separateroutes to each product.
PB American Chemical Society
SN 0276-7333
SN 1520-6041 (electrónico)
YR 2017
FD 2017
LK http://hdl.handle.net/10272/16190
UL http://hdl.handle.net/10272/16190
LA eng
NO Fructos, 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.6b00604
NO We thank the Spanish MINECO for CTQ2014-52769-C3-1-R, CTQ2014-57761-R, RED INTECAT CTQ2014-52974-REDC and Severo Ochoa Excellence Accreditation 2014-2018 SEV-2013-0319 and the ICIQ Foundation for financial support.
DS Repositorio Institucional de la Universidad de Huelva
RD 14 jul 2026