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Ag(I)-Catalyzed C–H Activation: The Role of the Ag(I) Salt in Pd/Ag-Mediated C–H Arylation of Electron-Deficient Arenes

Whitaker, D; Burés, J; Larrosa, I; (2016) Ag(I)-Catalyzed C–H Activation: The Role of the Ag(I) Salt in Pd/Ag-Mediated C–H Arylation of Electron-Deficient Arenes. Journal of the American Chemical Society , 138 (27) pp. 8384-8387. 10.1021/jacs.6b04726. Green open access

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Abstract

The use of stoichiometric Ag(I)-salts as additives in Pd-catalyzed C–H functionalization reactions is widespread. It is commonly proposed that this additive acts as an oxidant or as a halide scavenger promoting Pd-catalyst turnover. We demonstrate that, contrary to current proposals, phosphine ligated Ag(I)-carboxylates can efficiently carry out C–H activation on electron-deficient arenes. We show through a combination of stoichiometric and kinetic studies that a (PPh3)Ag-carboxylate is responsible for the C–H activation step in the Pd-catalyzed arylation of Cr(CO)3-complexed fluorobenzene. Furthermore, the reaction rate is controlled by the rate of Ag(I)-C–H activation, leading to an order zero on the Pd-catalyst. H/D scrambling studies indicate that this Ag(I) complex can carry out C–H activation on a variety of aromatic compounds traditionally used in Pd/Ag-mediated C–H functionalization methodologies.

Type: Article
Title: Ag(I)-Catalyzed C–H Activation: The Role of the Ag(I) Salt in Pd/Ag-Mediated C–H Arylation of Electron-Deficient Arenes
Open access status: An open access version is available from UCL Discovery
DOI: 10.1021/jacs.6b04726
Publisher version: https://doi.org/10.1021/jacs.6b04726
Language: English
Additional information: This version is the author accepted manuscript. For information on re-use, please refer to the publisher’s terms and conditions.
UCL classification: UCL
UCL > Provost and Vice Provost Offices
UCL > Provost and Vice Provost Offices > UCL BEAMS
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences
UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry
URI: https://discovery.ucl.ac.uk/id/eprint/10057980
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