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Nine pairs of cone and 1,3-alternate calix[4]arenes having distal propargyl or 2-azidoethyl groups at their phenolic oxygens were thoroughly studied at macrocyclization under copper(I) catalysis (CuAAC, copper(I)-catalyzed azide-alkyne cycloaddition). Though...

Copper(I)-catalyzed addition of limited amounts of azides to multiple alkynes, which led to statistical mixtures of triazole/acetylene derivatives or, in other cases, resulted in preferred formation of multiple triazoles, was studied at pre-organizable calixarene platforms bearing up to four propargyl groups. Depending on calixarene structures and reaction conditions, the unprecedented specific or selective formation of exhaustively triazolated calixarenes or a complete loss of the selectivity were observed. Both autocatalytic copper activation and a local copper(I) concentration increase due to copper-triazole complexation were thoroughly studied as the most expected reasons for the selectivity and both were disproved. Mixed triazolated/propargylated calixarenes and their copper(I) complexes proved not to be involved in the cascade-like process that was modeled to be driven by an intramolecular transfer of two copper(I) ions from a just-formed binuclear copper intermediate to the adjacent acetylene unit.