Starting from macrocycle (S)-1b, rotaxanes 5 and 6, which are derived from alkyne precursors less sterically bulky than alkyne 2, and rotaxane 7, derived from a less sterically bulk aryl azide than 3, were produced in reasonable stereochemical purity (78%, 48% and 78% de respectively as judged by 1 H NMR analysis of the crude reaction products). If instead macrocycle (S)-1e was employed, after reduction of the crude reaction product, rotaxanes 5, 6 and 7 were produced in significantly enhanced diastereomeric purity (>96%, 92% and >96% de respectively), and reasonable isolated yield. Both macrocycles produced the same major stereoisomer of the product. Based on this, and the similarity between the observed stereoselectivity with (S)-1e in the synthesis of rotaxane 4e, we tentatively assign the major stereoisomers produced to have the same relative orientation of axle and macrocycle, as shown. Rotaxanes 5-9 were produced from (S)-1b or (S)-1e under the conditions shown in Figure , except 8 and 9 which were synthesized in CHCl3-EtOH (1 : 1), with subsequent reduction in the case of (S)-1e (see ESI for further details). b Determined by 1 H NMR analysis of the crude reaction product. Determined by 1 H NMR analysis of the purified material.