In conclusion, we have demonstrated that by placing a simple and readily removed amino acid derived chiral auxiliary on a bipyridine macrocycle we can prepare mechanically planar chiral rotaxanes and catenanes in which the mechanical bond provides the sole stereogenic unit in excellent enantiopurity. Importantly, our results suggest that macrocycle 1e can produce interlocked products in excellent stereoselectivity even when the steric demand of the alkyne and azide substrates is reduced. The same relative disposition of alkyne and azide components was observed in the three examples that were characterized by SCXRD, which suggests that 1e has a reliable preference in terms of the major stereoisomer produced. Our results suggest that 1e, and perhaps chiral macrocycles more generally, have significant potential for the synthesis of more complicated mechanically chiral interlocked structures. Indeed, we demonstrated the flexibility of this approach through the stereoselective synthesis of all three stereoisomers of a co-conformationally mechanically planar chiral [3]rotaxane, the first time to our knowledge that this has been achieved. Our results suggest that it will be possible to design chiral macrocycles for use in the active template approach, 11 and perhaps also passive template methodologies, 28 that allow large families of mechanically chiral molecules to be prepared readily from simple, achiral building blocks. We anticipate that this will dramatically accelerate the investigation of mechanically chiral molecules in a range of applications at a time when their potential in catalysis, 22 sensing 3 and as chiroptical switches, and their chiroptical properties and unusual stereochemistry 31 is increasing.