Palladium-catalyzed allylic amination via p-allylpalladium intermediate is a powerful method for the synthesis of allylamines. The direct catalytic amination of unactivated allylic alcohols with the amines is promoted by using Pd[P(OPh)3]4 as a catalyst. This transformation was applied to the synthesis of a variety of diallylated products in good to excellent yield. The kinetic deuterium isotope effect of allylic amination reactions were examined with deuterated alcohol and aniline. The rate dependence for the disappearance of aniline was dependent on Pd[P(OPh)3]4 and allylic alcohol. This suggested that formation of the p-allylpalladium intermediate is involved in a rate-determining step. In order to obtain activation parameters, the reaction has been carried out at different temperatures (323-343 K). Studies aimed at elucidating the mechanism of palladium-catalyzed allylic amination will be discussed in detail.

Mechanistic studies and synthetic applications of palladium-catalyzed direct aminations of allylic alcohols

245th National Meeting (2013)

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