Repurposing Aryl Boronic Acids as Halogen‐Atom Transfer Agents

Halogen‐atom transfer (XAT) is an important method for the generation of carbon radicals. Hence, the development of new XAT agents has emerged as an important research avenue in organic synthesis. Aryl radicals are particularly promising XAT agents but have witnessed limited application. Herein, we introduce a protocol that repurposes widely available aryl boronic acids as XAT agents for alkyl iodide activation. We exemplify this concept on a Giese reaction, constructing valuable, sp 3 ‐rich scaffolds. The reaction is highly efficient and tolerant of a variety of sensitive functional groups. Furthermore, we showcase the compatibility of our boronic acid XAT agents in processes based on the use of transition metals, like cobalt for desaturative purposes.