The oxidative coupling of arenes via double C�H activation would constitute the ideal method for the construction of biaryls, both in terms of step- and atom-economy. Advances in this direction, however, are hindered by the enormous challenge of controlling the selectivity in the two individual C�H activation steps (scheme, left), necessary to favour cross-coupling over the two possible homo-coupling products.1Our proposed solution to this challenge involves a designed catalytic cycle in which the two consecutive C�H activation steps are performed by two Au species in different oxidation states (scheme, right). The orthogonal selectivity of Au(I) and Au(III) complexes, which display high substrate selectivity for electron-deficient2 and electron-rich3 arenes, respectively, allows obtaining complete selectivity for cross-coupling.4(1) (a) Cho, S. H.; Kim, J. Y.; Kwak, J.; Chang, S. Chem. Soc. Rev. 2011  , 40, 5068; (b) Liu, C.; Zhang, H.; Shi, W.; Lei, A. Chem. Rev. 2011  , 111, 1780.(2) (a) Lu, P.; Boorman, T. C.; Slawin, A. M. Z.; Larrosa, I. J. Am. Chem. Soc. 2010  , 132, 5580; (b) Ahlsten, N.; Perry, G. J. P.; Cambeiro, X. C.; Boorman, T. C.; Larrosa, I. Catal. Sci. Technol. 2013  , 3, 2892.(3) Boorman, T. C.; Larrosa, I. Chem. Soc. Rev. 2011  , 40, 1910.(4) Cambeiro, X. C.; Boorman, T. C.; Lu, P.; Larrosa, I. Angew. Chem. Int. Ed. 2013  , 52, 1781.

Redox control of selectivity for a Au-catalysed oxidative cross-coupling of arenes via double C�H activation

248th National Meeting (2014)

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