Institute of Chemical Research of Catalonia (ICIQ), Avgda. Països Catalans 16, 43007 Tarragona, Spain.
Chem Commun (Camb). 2013 Nov 18;49(89):10486-8. doi: 10.1039/c3cc44648d.
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 η(1)-superoxocopper(ii), μ-η(2):η(2)-peroxodicopper(ii) and bis(μ-oxo)-dicopper(iii).
通过 DFT 计算确定了铜（i）催化末端炔烃的氧化有氧三氟甲基化的反应机理。CF3（-）与铜的转金属似乎是一个配体取代过程，与金属无关。氧气的活化遵循顺序η（1）-超氧合铜（ii）、μ-η（2）：η（2）-过氧二铜（ii）和双（μ-氧）-二铜（iii）。
