Nucleophilic Radicals as Hydrogen Atom Abstractors in C(sp3)‐H Functionalization Reactions

Comprehensive Summary Hydrogen atom transfer (HAT) is an elementary mechanistic step in organic synthesis. The photoredox‐catalyzed HAT has transformed organic synthesis by enabling the activation and subsequent cross‐coupling of traditionally inert yet ubiquitous C(sp 3 )‐H bonds. While diverse electrophilic radical species have proven to be exceptionally effective HAT catalysts for selective functionalization of hydridic and electron‐neutral C(sp 3 )‐H, general methods using nucleophilic radicals as hydrogen atom abstractors in C(sp 3 )‐H functionalization remain relatively underdeveloped. Herein, we highlight two creative and strategic advances in addressing this long‐standing challenge, and emphasize reaction achievements, mechanistic insights, potential, and future challenges.