Palladium-Assisted Amination of Olefins. A Mechanistic Study

Article abstract of DOI:10.1021/ja00335a042

The mechanism of the palladium-assisted amination of olefins has been studied by low-temperature NMR and ultraviolat spectroscopy, conductivity measurements, and stoichiometry and exchange studies.The specific sequence of steps followed strongly depends on the temperature of amine.With dimethylamine, the sequence consists of cleavage of the chloride bridge by the amine to give a single olefin-palladium-amine complex (2).This undergoes amination of the olefin and concomitant cyclization to form the β-aminoalkylpalladium complex (3) directly and dimethylammonium hydrochloride.In contrast, with diethylamine, the initially formed olefin-palladium-amine complex undergoes amination to form a discrete zwitterionic complex (6).This reacts slowly with additional added amine to give the chelating β-aminoalkylpalladium complex (7).