Atomically Dispersed Iron‐Catalyzed Aerobic Hydroxylation of Allylic and Propargylic C─H Bonds

ABSTRACT Selective functionalization of carbon–hydrogen bonds represents a central goal in modern organic synthesis, yet achieving site‐ and chemoselective oxidation using molecular oxygen remains a longstanding challenge. In particular, aerobic hydroxylation of allylic and propargylic C─H bonds is difficult due to overoxidation and competing side reactions. Here we report a heterogeneous catalyst featuring atomically dispersed iron sites embedded in a nitrogen‐doped carbon matrix. This catalyst enables unprecedented site‐ and chemoselective allylic and propargylic C─H hydroxylation of alkenes and alkynes using air as the oxidant at 30°C. The method accommodates a broad range of terminal and internal substrates with excellent functional‐group tolerance and enables late‐stage oxidation of structurally complex molecules. Mechanistic studies demonstrate that the catalytic activity originates from highly dispersed FeN x sites. This work highlights the potential of single‐atom catalysis to address fundamental challenges in sustainable C─H oxidation and expands the toolbox for selective oxidative transformations.