Radical Brook Rearrangements: Concept and Recent Developments

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The Brook rearrangement has already become established as one of the most important molecular rearrangements in synthetic chemistry and has been applied in the generation of complexes, drug discovery, material science, and natural products synthesis. Compared to the widely known ionic mechanism, the radical Brook rearrangement is less explored because of the difficulty in generating alkoxyl radical species. This Minireview summarizes the early developments and general concept of the radical Brook rearrangement and highlights recent advances in photocatalytic reactions and transition‐metal‐catalyzed cross‐coupling reactions involving radical Brook rearrangements. We hope this survey will inspire further developments in this emerging area.