A divergent mechanistic course of Pd(0)-catalyzed aza-claisen rearrangement and aza-rautenstrauch-type cyclization of N -allyl ynamides

Article abstract of DOI:10.1021/ol100446p

A fascinating mechanistic study of ynamido-palladium-allyl complexes is described that features isolation of a unique silyl ketenimine via aza-Claisen rearrangement, which can be accompanied by an unusual thermal N-to-C 1,3-Ts shift in the formation of tertiary nitriles and a novel cyclopentenimine formation via a palladium-catalyzed aza-Rautenstrauch-type cyclization pathway.