Nickel-, Palladium-, and Platinum-Catalyzed Reactions of Perfluoro- and Polyfluoroalkyl Iodides with Tertiary Amines

Article abstract of DOI:10.1021/jo00392a010

The relative catalytic activities of Ni group metals in the reactions of perfluoroalkyl and polyfluoroalkyl iodides with tertiary amines to give enamines were compared, giving a reactivity order Ni > Pd > Pt, which parallels the order of the first ionization potential of the three metals.In comparing the Ni-catalyzed reaction of iodide 1 with tertiary amines containing zero to three methyl groups, it was found that in the case of trimethylamine only the reduced product 4 was formed, while the other three types of tertiary amines produced enamines (19, 21, 23) as wellas 4.The chemoselectivity of this reaction was studied.A mechanism is proposed for the reaction.Acid hydrolysis of (fluoroalkyl)enamines afforded enaminones or aldehydes depending upon the presence or absence of an alkyl group at the β-carbon.