In conclusion, we have demonstrated that type 1 rotaxane mechanical geometric isomers and mechanically axially chiral enantiomers can be obtained by controlling facial selectivity in an AT-CuAAC synthesis. Specifically, we show that an H-bonding interaction between a prochiral macrocycle and a functional group unsymmetrically disposed in the corresponding half-axle (rotaxane synthesis) or pre-macrocycle (catenane synthesis) is sufficient to control the reaction outcome. The high selectivity observed with optimized substrates allowed us to design a direct enantioselective synthesis of mechanically axially chiral rotaxanes, only the second 31a example of a direct stereoselective synthesis of a mechanically chiral molecule and the first of this recently identified stereogenic unit. To date, type 1 mechanical geometric isomers of rotaxanes based on calixarenes and similar coneshaped macrocycles, 5,6b,7d,e as well as structures expressing combinations of mechanical and covalent stereochemistry 4h have been investigated as components of molecular switches and motors. Here we have demonstrated that such isomerism can be expressed and controlled in much simpler macrocycles, opening new motifs for study. Similarly, mechanically planar chiral molecules, for which stereoselective methods are known, have been investigated as enantioselective sensors, 28 catalysts, and chiroptical switches. With methodological concepts now in hand to efficiently synthesize their mechanically axially chiral cousins in high stereopurity, we eagerly anticipate the chemical applications to which molecules containing this stereogenic unit will soon be put.