Merging N‐Hydroxyphthalimide into Metal‐Organic Frameworks for Highly Efficient and Environmentally Benign Aerobic Oxidation

Abstract Two highly efficient metal‐organic framework catalysts TJU‐68‐NHPI and TJU‐68‐NDHPI have been successfully synthesized through solvothermal reactions of which the frameworks are merged with N ‐hydroxyphthalimide (NHPI) units, resulting in the decoration of pore surfaces with highly active nitroxyl catalytic sites. When t ‐butyl nitrite (TBN) is used as co‐catalyst, the as‐synthesized MOFs are demonstrated to be highly efficient and recyclable catalysts for a novel three‐phase heterogeneous oxidation of activated C−H bond of primary and secondary alcohols, and benzyl compounds under mild conditions. Based on the high efficiency and selectivity, an environmentally benign system with good sustainability, mild conditions, simple work‐up procedure has been established for practical oxidation of a wide range of substrates.