More excitingly, the high stereoselectivity observed in the AT-CuAAC reaction of azides 1 bearing a polarized NH presents the opportunity for the direct synthesis of MAC rotaxanes without the need for first forming separable co-conformational diastereomers; if the N substituent is too small to trap the macrocycle in one triazole-containing compartment, the only fixed stereochemistry in the product is provided by the MAC stereogenic unit.