Initial attempts to use a benzylic azide substrate under the same conditions failed; only trace amounts of rotaxane 8 could be detected by reaction with (S)-1b or (S)-1e. When the reaction solvent was replaced with CHCl3-EtOH (1 : 1), which has previously been employed in AT-CuAAC synthesis of catenanes, rotaxane 8 was produced from (S)-1e in high selectivity (>96% de) and moderate isolated yield (39%). The same reaction with macrocycle (S)-1b still resulted in low conversion and stereoselectivity (<5%, ~2% de). Finally, rotaxane 9, which is produced by reacting propargylic and benzyl azide half axles, was produced in low yield (30%) after a difficult purification but with excellent stereoselectivity (92% de), whereas macrocycle (S)-1b resulted in much lower stereoselectivity (8% de). Based on these preliminary results, the stereoselectivities of reactions involving macrocycle (S)-1e are remarkably unaffected by the steric demand of the alkyne and azide substrates, particularly when compared with our previously reported auxiliary methods.