Photoinduced Ligated Boryl Radical‐Mediated Functionalization of Organic Halides

Halogen atom transfers (XATs) represent a valuable class of reactions that facilitate the functionalization of CX bonds in alkyl and aryl halides. Historically, these transformations relied on tin‐ or silicon‐based reagents, which are plagued by several drawbacks, including toxicity, complex synthesis, and high costs. In response to these limitations, ligated boranes have recently emerged as a greener alternative, functioning as efficient halogen abstractors through the generation of reactive boryl radical species. This approach enables the selective and straightforward formation of alkyl and aryl radicals from their halide precursors, opening the door to a wide range of chemical transformations. This review highlights the most recent progress in ligated boryl radical‐mediated XAT chemistry, focusing on the variety of accessible reactions, the underlying mechanisms, and the mechanistic insights gained. To the best of the authors’ knowledge, this is the first comprehensive review dedicated to boryl radical‐mediated XAT processes. With growing interest in this area among synthetic chemists, the authors aim to provide both researchers and students with a clear overview of current advancements and inspire future exploration of ligated boryl radical chemistry.