Returning to our H-bonding-directed approach, when instead a propargylic amide was reacted with 2 to give 9, a significantly improved stereoselectivity (54% de) was obtained, which was reduced in EtOH (40% de). The corresponding N-methyl amide gave rise to rotaxane 10 in low selectivity (13% de). The AT-CuAAC coupling of 3 and an alkyl azide bearing a simple amide gave rotaxane 11 in moderate stereoselectivity (40% de), which was reduced in EtOH (19% de). Thus, the amide can be placed in either coupling partner. Finally, rotaxane 13, whose amide NH is expected to be more polarized than that of 12 was produced in good selectivity (72% de) at rt, which was improved (90% de) when the same reaction was conducted at -40 °C. Reducing the temperature further did not improve the observed stereocontrol and led to a slow reaction. Replacing the reaction solvent with EtOH once again led to reduced selectivity (26% de). As in the case of rotaxanes 4, the high selectivity observed in the synthesis of 9, 11 and 12 is consistent with the key role of an NH•••O interaction between the macrocycle and half-axle in controlling the facial selectivity in the AT-CuAAC reactions of macrocycle 2. However, we previously observed this interaction in the solid-state structures of both diastereomers of epimeric MAC catenanes due to the flexible nature of macrocycle 2. The major isomers of rotaxanes 9 and 11 determined by SCXRD (Figure and 3d respectively) highlight the importance of this flexibility; although both were formed selectively, counterintuitively the ring is oriented in opposite directions with respect to the amide in the major diastereomer of each. Thus, although the NH•••O interaction appears able to direct the synthesis of MGI-1 isomers, the major product depends on the detailed structure of the half-axles used. We also note that whereas an NH•••O interaction is observed in the SCXRD structure of 4d, in the case of 9 and 11 this is replaced by an NH•••N interaction between the amide proton and one of the bipyridine N atoms, with the SO unit instead interacting with the polarized C-H of the triazole moiety in an inter-or intra-molecular manner respectively, presumably because the NH unit is geometrically accessible to the macrocycle in rotaxanes 9 and 11 whereas it is not in the case of 4d.