Porous Aromatic Framework Covalently Embedded with N‐Hydroxyphthalimide as Metal‐free Heterogeneous Catalyst for Highly Efficient and Selective Aerobic Oxidation

Abstract Ideal catalysts with all‐around advantages including high efficiency and selectivity, environment‐benign and good recyclability, etc. have been long‐sought yet challenging. Herein, the stable porous aromatic framework covalently embedded with N ‐Hydroxyphthalimide (NHPI) organocatalytic site was constructed to establish an ideal catalytic system. The synthesized PAF‐NHPI catalyst was demonstrated to be metal‐free, highly efficient, selective, recyclable and heterogeneous for the aerobic oxidation of various alcohols, aldehydes, olefins, and hydrosilanes (totally 66 examples). As a proof‐of‐concept, the continuous PAF‐NHPI packed bed reactor achieved persistent conversion of 1‐phenylethanol to acetophenone up to 95 % yield. This work provides the inspiration for developing ideal catalysts in practical production of fine chemicals.