Enantioconvergent Synthesis of α‐Fluoroalkyl Alcohols Enabled by Photocatalytic Radical Brook Rearrangement

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While radical Brook rearrangement has emerged as a powerful strategy in modern organic synthesis, enantioselective cross coupling involving radical Brook rearrangement remains unexplored. Herein, we report a photocatalytic radical Brook rearrangement followed by cross‐coupling with aryl/heteroaryl bromides, enabling the enantioconvergent construction of chiral α‐fluoroalkyl alcohols. Key to this transformation is a radical relay process involving sequential generation of aryl cation radicals, alkoxy radicals, and carbon‐centered radicals through Brook rearrangement. The reaction exhibits exceptional scope (>40 examples), outstanding enantiocontrol (up to 99% ee), and broad functional group tolerance. The synthetic utility is demonstrated through formal syntheses of bioactive Odanacatib and LX‐1031, along with diverse downstream derivatizations.