A reaction mechanism for the copper(i)-catalyzed oxidative aerobic trifluoromethylation of terminal alkynes has been determined by DFT calculations. The transmetalation of CF3- to copper appears to be a ligand replacement process independent of the metal. The dioxygen activation follows the sequence η1-superoxocopper(ii), μ-η2:η2-peroxodicopper(ii) and bis(μ-oxo)-dicopper(iii). © 2013 The Royal Society of Chemistry.
|Publication status||Published - 18 Nov 2013|