Halogen‐Bridged Methylnaphthyl Palladium Dimers as Versatile Catalyst Precursors in Coupling Reactions

Halogen‐bridged methylnaphthyl (MeNAP) palladium dimers are presented as multipurpose Pd‐precursors, ideally suited for catalytic method development and preparative organic synthesis. By simply mixing with phosphine or carbene ligands, they are in situ converted into well‐defined monoligated complexes. Their catalytic performance was benchmarked against state‐of‐the‐art systems in challenging Buchwald–Hartwig, Heck, Suzuki and Negishi couplings, and ketone arylations. Their use enabled record‐setting activities, beyond those achievable by optimization of the ligand alone. The MeNAP catalysts permit syntheses of tetra‐ortho‐substituted arenes and bulky anilines in near‐quantitative yields at room temperature, allow mono‐arylations of small ketones, and enable so far elusive cross‐couplings of secondary alkyl boronic acids with aryl chlorides.