Novel amido-enaminone threads serve as efficient templates for the assembly of hydrogen-bonded [2]rotaxanes, enabling versatile post-synthetic modifications. Benzyl groups on the amido moiety allow for diastereoselective intramolecular cyclizations, yielding interlocked β-lactams. The enaminone motif makes possible the stopper exchange while preserving the mechanical bond. Combining cyclization with one-pot stopper exchange and dethreading enables the stereoselective synthesis of highly functionalized non-interlocked lactams featuring a second heterocycle at their side chain via reactions with hydrazines or hydroxylamine
