Ag(I)-catalyzed C-H activation: the role of the Ag(I) salt in Pd/Ag mediated C-H arylation of electron-deficient arenes
File(s)Ag(I)-catalyzed C-H activation.pdf (779.91 KB)
Accepted version
Author(s)
Whitaker, D
Burés, J
Larrosa, I
Type
Journal Article
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.
Date Issued
2016-06-15
Date Acceptance
2016-05-07
Citation
Journal of the American Chemical Society, 2016, 138 (27), pp.8384-8387
ISSN
0002-7863
Publisher
American Chemical Society
Start Page
8384
End Page
8387
Journal / Book Title
Journal of the American Chemical Society
Volume
138
Issue
27
Copyright Statement
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/jacs.6b04726
Sponsor
Imperial College London
Subjects
Science & Technology
Physical Sciences
Chemistry, Multidisciplinary
Chemistry
PROGRESS KINETIC-ANALYSIS
METAL PI-COMPLEXATION
BOND FORMATION
FUNCTIONALIZATION
SELECTIVITY
ACETATE
POLYFLUOROARENES
HETEROCYCLES
PROPIONATE
REACTIVITY
General Chemistry
03 Chemical Sciences
Publication Status
Published