Palladium‐Catalyzed Allylic Alkylation with Phosphinoaryldihydrooxazole Ligands: First Evidence and NMR Spectroscopic Structure Determination of a Primary Olefin–Pd⁰ Complex

Under the 2D NMR spectroscopic magnifying glass: The intermediacy of 1 in the Pd-catalyzed allylic substitution was investigated and proven. Characterization of this Pd0 complex, which is primarily formed in the catalytic cycle, shows that attack of the nucleophile malonate at the double bond of the allyl ligand is preferred trans to the P atom.