Halide Perovskite Induces Halogen/Hydrogen Atom Transfer (XAT/HAT) for Allylic C-H Amination.
Angew Chem Int Ed Engl
; : e202413012, 2024 Sep 04.
Article
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| MEDLINE
| ID: mdl-39231037
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. CH2Cl2, CH2Br2) as mild oxidants for selective C-H allyl amination with 19,376 turnover. CsPbBr3 nanocrystals induce cooperative hydrogen-atom-transfer (HAT, C-H oxidation, and halogen-vacancy CsPbBr3-x formation) and halogen-atom-transfer (XAT, CsPbBr3-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.
Texto completo:
1
Colección:
01-internacional
Base de datos:
MEDLINE
Idioma:
En
Revista:
Angew Chem Int Ed Engl
Año:
2024
Tipo del documento:
Article
País de afiliación:
Estados Unidos
Pais de publicación:
Alemania