Palladium Catalysis for Aerobic Oxidation Systems Using Robust Metal–Organic Framework

Described here is a new and viable approach to achieve Pd catalysis for aerobic oxidation systems (AOSs) by circumventing problems associated with both the oxidation and the catalysis through an all‐in‐one strategy, employing a robust metal–organic framework (MOF). The rational assembly of a PdII catalyst, phenanthroline ligand, and CuII species (electron‐transfer mediator) into a MOF facilitates the fast regeneration of the PdII active species, through an enhanced electron transfer from in situ generated Pd0 to CuII, and then CuI to O2, trapped in the framework, thus leading to a 10 times higher turnover number than that of the homogeneous counterpart for Pd‐catalyzed desulfitative oxidative coupling reactions. Moreover, the MOF catalyst can be reused five times without losing activity. This work provides the first exploration of using a MOF as a promising platform for the development of Pd catalysis for AOSs with high efficiency, low catalyst loading, and reusability. Die Immobilisierung von PdII‐ und CuII‐Spezies in einem Metall‐organischen Gerüst (MOF) ermöglicht die Pd‐Katalyse für ein aerobes Oxidationssystem, eine desulfitierende oxidative Kupplung, mit hoher Effizienz, niedriger Katalysatorbeladung und Wiederverwendbarkeit. Man kann also einen PdII‐Katalysator, einen Liganden und einen Elektronentransfermediator in einem einzelnen MOF vereinen, um die Aktivität effizient und nachhaltig enorm zu steigern.