Mechanism of the Selective Fe-Catalyzed Arene Carbon-Hydrogen Bond Functionalization
-
Author
-
Publication Date
2018 -
Publisher
American Chemical Society -
Citation
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 -
Abstract
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. -
Project
info:eu-repo/grantAgreement/MINECO [CTQ2014-62234-EXP, CTQ2014-52769-C3-R-1, CTQ2014-54306-P, CTQ2014-52525-P, BES-2012-052801]
info:eu-repo/grantAgreement/Junta de Andalucia [P10-FQM-06292]
Fichero | Tamaño | Formato |
| Description |
---|---|---|---|---|
Mechanism of the Selective.pdf | 1.225Mb | View/ | versión post-print |
Fichero | Tamaño | Formato |
| Description |
---|---|---|---|---|
Mechanism of the Selective.pdf | 1.225Mb | View/ | versión post-print |