Journal of the American Chemical Society
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at close to stoichiometric ratio of arenes and without requir-
ing the use of directing groups. We envision the general
principles uncovered during this investigation will be appli-
cable for the successful development of other new useful
oxidative methodologies based on C–H activation. Although
the exact mechanism is still not clear, the scope and regiose-
lectivity of the electron-rich arenes are consistent with a
Au(III) C-H activation. The required presence of Ag for cata-
lytic turnover (Figure 2), suggests a possible involvement in
the C-H activation of the electron-poor arene.4d,20 Thorough
studies on the mechanism and the exact role of Ag in this
transformation are ongoing in our laboratory.
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ASSOCIATED CONTENT
Supporting Information
Detailed experimental procedures, characterization data of
1
all new compounds and copies of H, 13C and 19F NMR spec-
tra. This material is available free of charge via the Internet
(9) (a) Lu, P.; Boorman, T. C.; Slawin, A. M. Z.; Larrosa, I. J. Am.
Chem. Soc. 2010, 132, 5580–5581. (b) Gaillard, S.; Slawin A. M. Z. and
Nolan S. P. Chem. Commun. 2010, 46, 2742–2744. (c) Ahlsten, N.;
Perry, G. J. P.; Cambeiro, X. C.; Boorman, T. C.; Larrosa, I. Catal. Sci.
Technol. 2013, 2892-2897.
(10) (a) Cambeiro, X. C.; Boorman, T. C.; Lu, P.; Larrosa, I. Angew.
Chem. Int. Ed. 2013, 52, 1781–1784. (b) Hofer, M.; Nevado, C. Tetrahe-
dron 2013, 69, 5751–5757.
(11) (a) Wang, X.; Leow, D.; Yu, J.-Q. J. Am. Chem. Soc. 2011, 133,
13864–13867. (b) Hull, K. L.; Lanni, E. L.; Sanford, M. S. J. Am. Chem.
Soc. 2006, 128, 14047–14049. (c) Yeung, C. S.; Zhao, X.; Borduas, N.;
Dong, V. M. Chem. Sci. 2010, 1, 331–336.
AUTHOR INFORMATION
Corresponding Author
Author Contributions
‡ These authors contributed equally to this work.
ACKNOWLEDGMENT
We gratefully acknowledge the European Research Council
for a Starting Grant (to I.L.) and the Marie Curie Foundation
for Intra-European Fellowships (to X.C.C. and N.A.).
(12) (a) Racowski, J. M.; Ball, N. D.; Sanford, M. S. J. Am. Chem.
Soc. 2011, 133, 18022–18025. (b) Maleckis, A.; Kampf, J. W.; Sanford,
M. S. J. Am. Chem. Soc. 2013, 135, 6618−6625. (c) Canty, A. J.; Ariafard,
A.; Yates, B. F.; Sanford, M. S. Organometallics 2015, 34, 1085−1090.
(13) The more reactive and more electrophilic I(III) oxidant hy-
droxy(tosyloxy)iodobenzene (HTIB) resulted in poor mass recovery
Reaction of highly electron-rich arenes with HTIB has been previ-
ously described in a similar setting, giving place to diaryliodonium
compounds which were inactive in the Au-promoted cross-coupling.
Se ref 10a.
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