Beyond the traditional roles of Ag in catalysis: the transmetalating ability of organosilver(I) species in Pd-catalysed reactions

Silver salts are one of the most widely used additives in Pd-catalysed transformations. Apart from acting as halide scavenger and/or external oxidant, over the past decade it has been revealed that silver salts can play other roles such as C–H activation promoter or decarboxylating agent, generating organosilver(I) species. These nucleophiles can promote innovative transformations by reacting with PdII intermediates through a transmetalation step. This review article covers different Pd-catalysed C–C bond-forming reactions where silver complexes have been proposed to act as nucleophilic coupling partners. We will also provide relevant mechanistic features associated to these transformations.