Photocatalytic C(sp 3 ) radical generation via C-H, C-C, and C-X bond cleavage.

C(sp 3 ) radicals (R˙) are of broad research interest and synthetic utility. This review collects some of the most recent advancements in photocatalytic R˙ generation and highlights representative examples in this field. Based on the key bond cleavages that generate R˙, these contributions are divided into C-H, C-C, and C-X bond cleavages. A general mechanistic scenario and key R˙-forming steps are presented and discussed in each section.