More recently, we identified that when a facially dissymmetric macrocycle encircles a prochiral axle an overlooked mechanically axially chiral (MAC) 12 stereogenic unit arises that is analogous to that of catenanes identified by Wasserman and Frisch over 60 years earlier. Having made this observation, we demonstrated that such molecules can be synthesized using a diastereoselective co-conformational chiral auxiliary active template Cu-mediated alkyne-azide cycloaddition (AT-CuAAC ) approach with a ring whose facial dissymmetry arises from a single prochiral sulfoxide unit.