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

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. CHCl, CHBr) as mild oxidants for selective C-H allyl amination with 19,376 turnovers. CsPbBr nanocrystals induce cooperative hydrogen-atom-transfer (HAT, C-H oxidation, and halogen-vacancy CsPbBr formation) and halogen-atom-transfer (XAT, CsPbBr-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.