Silver-Based Radical Reactions: Development and Insights

Silver-mediated reactions have recently emerged as a frontier area in organic chemistry. Indeed, the remarkable property of silver as a single- electron oxidant has led to its exploitment into the field of radical chemistry. The excellent reactivity and high selectivity exhibited by silver salts in the ac- tivation of different organic substrates place them among the most prominent reagents in free radical reactions. The present review aims to provide the readers with a critical overview of silver-based radi- cal reactions, especially emphasizing the reactivity, selectivity and a detailed description of the reaction mechanism with particular attention to the role of Ag(I)-based catalysts/reactants. The selected exam- ples have been classified according to the type of radicals generated, namely carbon-centered radicals and heteroatom (such as nitrogen, oxygen, phospho- rus, sulfur)-centered radicals. The generation of such radicals as well as their application in synthetic pro- cesses including oxidation, addition, coupling, and radical cascades have been described in detail.