Synthetic Applications of Photochemically Generated Radicals from Protic C(sp3)−H Bonds

Abstract The utilization of photo‐induced processes in C−H functionalization via radical pathways has emerged as a highly promising strategy for the preparation and modification of complex organic compounds. While current methods for generating carbon‐centred radicals from C−H bonds primarily focus on hydridic C−H bonds to yield nucleophilic radical species, the reactivity and potential applications of electrophilic radicals derived from protic C−H bonds remain largely unexplored. In this review, we aim to shed light on the seminal findings regarding the activation of protic C(sp 3 )−H bonds while also showcasing noteworthy examples of this radical formation process. Mechanistically diverse modes of activation are discussed, unified by proton‐coupled electron transfer (PCET) concepts.