A competing, dual mechanism for catalytic direct benzene hydroxylation from combined experimental-DFT studies
Vilella i Arribas, Laia (Universitat Autònoma de Barcelona. Departament de Química)
Conde, Ana (Universidad de Huelva. Departamento de Química)
Balcells, David 1978- (Universitetet i Oslo. Department of Chemistry)
Díaz-Requejo, M. Mar (Universidad de Huelva. Departamento de Química)
Lledós, Agustí (Lledós i Falcó) (Universitat Autònoma de Barcelona. Departament de Química)
Pérez, Pedro J. (Universidad de Huelva. Departamento de Química)

Date:	2017
Abstract:	A dual mechanism for direct benzene catalytic hydroxylation is described. A dual mechanism for direct benzene catalytic hydroxylation is described. Experimental studies and DFT calculations have provided a mechanistic explanation for the acid-free, Tp x Cu-catalyzed hydroxylation of benzene with hydrogen peroxide (Tp x = hydrotrispyrazolylborate ligand). In contrast with other catalytic systems that promote this transformation through Fenton-like pathways, this system operates through a copper-oxyl intermediate that may interact with the arene ring following two different, competitive routes: (a) electrophilic aromatic substitution, with the copper-oxyl species acting as the formal electrophile, and (b) the so-called rebound mechanism, in which the hydrogen is abstracted by the Cu-O moiety prior to the C-O bond formation. Both pathways contribute to the global transformation albeit to different extents, the electrophilic substitution route seeming to be largely favoured.
Grants:	European Commission 618303 Ministerio de Economía y Competitividad CTQ2014-54071-P Ministerio de Economía y Competitividad CTQ2014-52769-C3-1-R
Rights:	Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, fins i tot amb finalitats comercials, sempre i quan es reconegui l'autoria de l'obra original.
Language:	Anglès
Document:	Article ; recerca ; Versió publicada
Published in:	Chemical science, Vol. 8, issue 12 (October 2017) , p. 8373-8383, ISSN 2041-6539

DOI: 10.1039/c7sc02898a
PMID: 29619184

11 p, 1.3 MB

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