Silver‐Based Radical Reactions: Development and Insights

Abstract 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 activation 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 radical 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 examples have been classified according to the type of radicals generated, namely carbon‐centered radicals and heteroatom (such as nitrogen, oxygen, phosphorus, sulfur)‐centered radicals. The generation of such radicals as well as their application in synthetic processes including oxidation, addition, coupling, and radical cascades have been described in detail. magnified image