Palladium-Catalyzed Hydroaminocarbonylation of Olefins with Aliphatic Amines without Additives

Palladium-catalyzed hydroaminocarbonylation reactions of olefins using aliphatic amines were performed under carbon monoxide atmosphere. Despite the strong basicity of the applied nucleophiles, the targeted amides were successfully synthesized in the absence of acidic additives. Styrene, oct-1-ene and isoprene were transformed to the corresponding amide isomers in moderate to good isolated yields under optimized reaction conditions. Various aliphatic amines were used as N-nucleophiles. The effect of chiral diphosphines on product distribution, that is, on chemo-, regio- and enantioselectivities was also studied. Plausible explanation was given for the additive-free hydroaminocarbonylation reaction.