Sulfonium Salts as Acceptors in Electron Donor‐Acceptor Complexes

The photoactivation of electron donor‐acceptor complexes has emerged as a sustainable, selective and versatile strategy for the generation of radical species. Electron donor‐acceptor (EDA) complexation, however, imposes electronic constraints on the donor and acceptor components and this can limit the range of radicals that can be generated using the approach. New EDA complexation strategies exploiting sulfonium salts allow radicals to be generated from native functionality. For example, aryl sulfonium salts, formed by the activation of arenes, can serve as the acceptor components in EDA complexes due to their electron‐deficient nature. This “sulfonium tag” approach relaxes the electronic constraints on the parent substrate and dramatically expands the range of radicals that can be generated using EDA complexation. In this review, these new applications of sulfonium salts will be introduced and the areas of chemical space rendered accessible through this innovation will be highlighted. Photoactivation of electron donor‐acceptor (EDA) complexes is a sustainable, selective and versatile strategy for the generation of radicals. Sulfonium salt acceptors promise to dramatically expand the range of radicals that can be generated and exploited using EDA chemistry; the use of readily installed “sulfonium tags” relaxes the electronic constraints typically imposed on the parent substrate by an EDA complexation approach.