RT Journal Article
T1 Mechanism of the Selective Fe-Catalyzed Arene Carbon-Hydrogen Bond Functionalization
A1 Postils, Verònica
A1 Rodríguez, Mònica
A1 Sabenya, Gerard
A1 Conde Alcántara, Ana Isabel
A1 Díaz Requejo, María Mar
A1 Pérez Romero, Pedro José
A1 Costas, Miquel
A1 Solà, Miquel
A1 Luis, Josep M.
AB The complete chemoselective functionalization of aromatic C(sp(2))-H bonds of benzene and alkyl benzenes by carbene insertion from ethyl diazoacetate was unknown until the recent discovery of an iron-based catalytic system toward such transformation. A Fe(II) complex bearing the pytacn ligand (pytacn = L1 = 1-(2-pyridylmethyl)-4,7-dimethyl-1,4,7-triazacyclononane) transferred the CHCO2Et unit exclusively to the C(sp(2))-H bond. The cycloheptatriene compound commonly observed through Buchner reaction or, when employing alkyl benzenes, the corresponding derivatives from C(sp(3))-H functionalization are not formed. We herein present a combined experimental and computational mechanistic study to explain this exceptional selectivity. Our computational study reveals that the key step is the formation of an enol-like substrate, which is the precursor of the final insertion products. Experimental evidences based on substrate probes and isotopic labeling experiments in favor of this mechanistic interpretation are provided.
PB American Chemical Society
SN 2155-5435
YR 2018
FD 2018
LK http://hdl.handle.net/10272/15970
UL http://hdl.handle.net/10272/15970
LA eng
NO Postils, V., Rodríguez, M., Sabenya, G., Conde, A., Díaz-Requejo, M. M., Pérez, P. J., Costas, M., Solà, M., Luis, J. M. (2018). Mechanism of the Selective Fe-Catalyzed Arene Carbon–Hydrogen Bond Functionalization. ACS Catalysis, 8(5), 4313-4322. https://doi.org/10.1021/acscatal.7b03935
NO Support for this work was provided by the MINECO (Grants CTQ2014-62234-EXP, CTQ2014-52769-C3-R-1, CTQ2014-54306-P, CTQ2014-52525-P, and Grant BES-2012-052801 to V.P.), the Junta de Andalucia (Grant P10-FQM-06292) and the Generalitat de Catalunya (Grants 2017SGR39 and 2017SGR264, Xarxa de Referencia en Quimica Teorica i Computacional, ICREA Academia prizes 2013 to M.C. and 2014 to M.S.). The EU under the FEDER grant UNGI10-4E-801 (European Fund for Regional Development) has also funded this research.
DS Repositorio Institucional de la Universidad de Huelva
RD 31 may 2026