A competing, dual mechanism for catalytic direct benzene hydroxylation from combined experimental-DFT studies

Laia Vilella, Ana Conde, David Balcells, M. Mar Díaz-Requejo, Agustí Lledós, Pedro J. Pérez

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10 Citations (Scopus)

Abstract

© 2017 The Royal Society of Chemistry. A dual mechanism for direct benzene catalytic hydroxylation is described. Experimental studies and DFT calculations have provided a mechanistic explanation for the acid-free, TpxCu-catalyzed hydroxylation of benzene with hydrogen peroxide (Tpx = 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.
Original languageEnglish
Pages (from-to)8373-8383
JournalChemical Science
Volume8
Issue number12
DOIs
Publication statusPublished - 1 Jan 2017

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