Pre-macrocycle (S)-7 was subjected to the AT-CuAAC reaction with macrocycle 2. The product, topologically chiral [2]catenane 8, was isolated as a mixture of diastereomers (90% de), as judged by 1 H NMR (Figure ). By analogy with catenane 3b, which seems reasonable given the similarities of the functional groups reacting and the similar stereoselectivity obtained, the major isomer is tentatively assigned as (S,Smt)-8. Reduction and decarbonylation of (S,Smt)-8 yielded [2]catenane 9, which contains no previously described stereogenic unitsthe molecule lacks any covalent stereogenic units, and the triazole containing macrocycle is not oriented and so the system does not conform to the definition of a topologically chiral catenane. Nevertheless, whereas the compounds produced from 10 and (S,Smt)-8 produce identical 1 H NMR spectra, the latter is clearly highly enantioenriched, whereas the former is racemic as judged by CSP-HPLC analysis (Figure ), which indicates that catenane 9 was formed from (S,Smt)-8 in 88% ee, and circular dichroism spectroscopy (Figure ).