TY - JOUR
T1 - A competing, dual mechanism for catalytic direct benzene hydroxylation from combined experimental-DFT studies
AU - Vilella, Laia
AU - Conde, Ana
AU - Balcells, David
AU - Mar Díaz-Requejo, M.
AU - Lledós, Agustí
AU - Pérez, Pedro J.
PY - 2017/1/1
Y1 - 2017/1/1
N2 - © 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.
AB - © 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.
U2 - https://doi.org/10.1039/c7sc02898a
DO - https://doi.org/10.1039/c7sc02898a
M3 - Article
VL - 8
SP - 8373
EP - 8383
JO - Chemical Science
JF - Chemical Science
SN - 2041-6520
IS - 12
ER -