Schiff bases, despite their structural versatility and broad applications, have remained elusive as acyclic atropisomers due to synthetic challenges. Herein, we report a palladium-catalyzed asymmetric N-allylation of diarylmethanimines with allylic precursors, enabling the construction of acyclic Schiff base atropisomers bearing C–C axes. Crucially, dynamic ligand exchange between the imine substrates and the palladium pre-catalyst drives its evolution from a less active to a more reactive speci