Halide Perovskite Induces Halogen/Hydrogen Atom Transfer (XAT/HAT) for Allylic C−H Amination

Abstract Allylic C−H amination has emerged as a powerful tool to construct allylamines, common motifs in molecular therapeutics. Such reaction implies an oxidative path for C−H activation but furnishes reductive amines, inferring mild oxidants’ inactivity for C−H oxidation but strong oxidants’ detriment to products. Herein we report a heterogeneous catalytic approach that manipulates halogen‐vacancies of perovskite photocatalyst and exploits halogenated‐solvents (i.e. CH 2 Cl 2 , CH 2 Br 2 ) as mild oxidants for selective C−H allyl amination with 19,376 turnovers. CsPbBr 3 nanocrystals induce cooperative hydrogen‐atom‐transfer (HAT, C−H oxidation, and halogen‐vacancy CsPbBr 3−x formation) and halogen‐atom‐transfer (XAT, CsPbBr 3−x ‐induced solvent reduction) under a radical chain mechanism. Terminal/internal olefins are amenable to forge aromatic/aliphatic, cyclic/acyclic, secondary/tertiary allylamines (70 examples), including drugs or their derivatives.