Boron in Radical Chemistry

Abstract This article focuses on the main synthetic applications of boron derivatives in radical‐mediated reactions. Organoboranes represent a unique source of alkyl radicals that are commonly used for radical initiation, for stoichiometric generation of radicals, and as a reagent to sustain radical chain processes. The use of boron derivatives in reductive processes has exploded during the last years. This chemistry takes advantage of the Lewis acidic character of boron derivatives and its unique reactivity toward heteroatom‐centered radicals. Finally, boron‐containing moieties represent useful functional groups that activate radicals and radical traps and offer opportunities for further elaboration of complex molecular architectures.