Photoinduced Transition‐Metal and External Photosensitizer Free Benzylic Fluorination of Unactivated Alkylarenes

Abstract A green and efficient protocol for the direct monofluorination of unactivated alkylarenes under visible‐light irradiation has been developed, without any extraneous transition‐metal catalysts or photosensitizers. This method is compatible with a broad spectrum of functional groups, including carboxylic and alcoholic scaffolds, under mild reaction conditions. Gram‐scale synthesis of a fluorine‐containing pharmaceutical analogue was successfully executed, underscoring the strategy's reliability and practicality. Furthermore, mechanistic studies suggest that a single‐electron transfer mechanism might be responsible for the generation of the benzylic radicals in initiation step.