The palladium-catalysed “metallo-ene” step in a cyclisation/β-elimination reaction sequence has been shown to be suprafacial with respect to the olefinic component. This reaction has been applied to the synthesis of a trisubstituted exocyclic alkenyl pyrrolidine with complete stereocontrol. The palladium(0)-mediated addition of allylic acetates to (E)- or (Z)-substituted alkenes was shown to proceed with complete stereocontrol.