Synthesis of trifluoromethylthiolated azacalix[1]arene[3]pyridines from the Cu(ii)-mediated direct trifluoromethylthiolation reaction of arenes via reactive arylcopper(iii) intermediates

Abstract

Using azacalix[1]arene[3]pyridines and their high valent organocopper(II) and (III) complexes as probes, arene C–H bond trifluoromethylthiolation was investigated. While arylcopper(II) compounds appeared almost inert, arylcopper(III) compounds reacted efficiently with a nucleophilic trifluoromethylthiolating reagent. Under mild conditions, azacalix[1]arene[3]pyridines underwent the regioselective Cu(ClO₄)₂-mediated one-pot trifluoromethylthiolation reaction with Me₄NSCF₃ to afford low-rim functionalized macrocycles.