| A series of arylpalladium alkyl complexes containing varied functional groups alpha to the metal was prepared to reveal the effect of ligand steric and electronic properties on structure, stability, and reactivity. Arylpalladium complexes of methyl, benzyl, enolate, cyanoalkyl, and trifluoroethyl groups underwent carbon-carbon bond-forming reductive elimination upon heating. Mechanistic studies of the reductive elimination process led to the discovery of a new coupling reaction, the palladium-catalyzed alpha-arylation of nitriles, and to the development of improved methods for the palladium-catalyzed synthesis of alpha-aryl amides. |
