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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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Supplementary files

Article information


Submitted
30 Jun 2017
Accepted
04 Oct 2017
First published
05 Oct 2017

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2017,8, 8373-8383
Article type
Edge Article

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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