A Review on Photo‐Decarboxylative Fluorination, a Mechanistic Framework

Abstract

The formation of C─F bonds remains a central challenge in modern synthesis, where fluorine incorporation underpins advances in pharmaceuticals, agrochemicals, radiochemistry, and functional materials. Photo‐decarboxylative fluorination has rapidly emerged as a powerful and sustainable strategy for C─F bond formation, enabling direct conversion of abundant carboxylic acids into valuable fluorinated motifs under visible‐light irradiation. Recent progress has revealed four distinct yet complementary activation modes for fluorine atom transfer (FAT), radical–polar crossover (RPC), ligand‐to‐metal charge transfer (LMCT), and electron donor–acceptor (EDA) complex excitation that collectively broaden the accessible chemical space, from aliphatic and benzylic frameworks to challenging aryl substrates. These mechanistic paradigms offer exceptional functional group tolerance, mild operational conditions, and compatibility with late‐stage diversification, radiochemical labeling, and polymer upcycling. This review provides an integrated overview of these activation platforms, highlighting key mechanistic principles, catalytic strategies, and synthetic applications that define the growing impact of photo‐decarboxylative fluorination in contemporary fluorine chemistry.