Recent advances in the intermolecular addition of carbonyloxy radicals to alkenes

Abstract

Oxygen-centered radicals are highly reactive intermediates that serve key roles in radical-mediated organic transformations. Carbonyloxy radicals, a distinct subset of oxygen-centered radicals, not only exhibit the general reactivity patterns of oxygen-centered species, such as hydrogen atom transfer (HAT) and β-scission, but also demonstrate unique behaviors attributed to their electrophilic ester group. In this review, we summarize recent progress in the intermolecular addition of aryl and alkoxy carbonyloxy radicals to alkenes through different precursors of carbonyloxy radicals. These transformations highlight novel esterification reactions, in which generally alcohols react with carboxylic acids, acyl chlorides, or acid anhydrides. We aim to inspire further exploration into the innovative esterification reactions enabled by carbonyloxy radical chemistry.