Halogenated difluoromethyl reagents serve as carbon synthons, finding applications in the construction of diverse molecular scaffolds and functional group modification reactions. Consequently, their conversion reactions and applications have attracted considerable attention. Recently, within the halogenated reagent cleavage paradigm dominated by electron transfer, its single‐cleavage, double‐cleavage, and multicleavage modes have yielded diverse synthetic building blocks. These have been applied in various radical reactions, facilitating the synthesis of numerous high‐value compounds and promoting the development of a series of highly efficient green synthetic methodologies. In this context, we review recent advances in photocatalysis‐dominated cleavage reactions of halogenated reagents, highlighting the recent achievements in this field.
Yao et al. (2026) studied this question.