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A directed heterogeneous C−H activation/halogenation reaction catalyzed by readily synthesized Pd@MOF nanocatalysts was developed. The heterogeneous Pd catalysts used were a novel and environmentally benign Fe-based metal-organic framework (MOF) (Pd@MIL-88B-NH2(Fe)) and the previously developed Pd@MIL-101-NH2(Cr). Very high conversions and selectivities were achieved under very mild reaction conditions and in short reaction times. A wide variety of directing groups, halogen sources, and substitution patterns were well tolerated, and valuable polyhalogenated compounds were synthesized in a controlled manner. The synthesis of the Pd-functionalized Fe-based MOF and the recyclability of the two catalysts are also presented. [ABSTRACT FROM AUTHOR]

The preparation of a Pd-functionalized Fe-based MOF is described together with its application in the title reaction and its recyclability. [ABSTRACT FROM AUTHOR]

The engaging prospect of mild and selective C−H activation has attracted many families of catalysts to join this quest. Metal‐organic frameworks (MOFs) may play one of the leading roles in the story. Small and finely dispersed palladium nanoparticles supported in MOFs catalyze the halogenation of aromatic C−H bonds efficiently and under some of the mildest conditions reported to date. Furthermore, subtle changes in the reaction conditions results in high control over the selectivity. More information can be found in the Full Paper by B. Martín‐Matute et al. on page 3729 ff. [ABSTRACT FROM AUTHOR]