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Issue 12, 2017
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A competing, dual mechanism for catalytic direct benzene hydroxylation from combined experimental-DFT studies

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Abstract

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.

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

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Publication details

The article was received on 30 Jun 2017, accepted on 04 Oct 2017 and first published on 05 Oct 2017


Article type: Edge Article
DOI: 10.1039/C7SC02898A
Citation: Chem. Sci., 2017,8, 8373-8383
  • Open access: Creative Commons BY license
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    A competing, dual mechanism for catalytic direct benzene hydroxylation from combined experimental-DFT studies

    L. Vilella, A. Conde, D. Balcells, M. M. Díaz-Requejo, A. Lledós and P. J. Pérez, Chem. Sci., 2017, 8, 8373
    DOI: 10.1039/C7SC02898A

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