Abstract The zwitterionic aza-Claisen rearrangement of optically active N-allylpyrrolidines and α-phenoxyacetyl fluorides proceeds with complete simple diastereoselectivity (internal asymmetric induction) and complete 1, 2-asymmetric induction to generate a new C–C bond adjacent to a chiral CN-Boc functionality. The resulting γ, δ-unsaturated amides were cyclised to give the corresponding pyrrolizidinones, which enabled the determination of ...