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A simple protocol to overcome the explosive pentafluoroethylation of carbonyl compounds by HFC-125 is described. The use of potassium (K) bases with triglyme or tetraglyme as a solvent safely yields the pentafluoroethylation products in good to high yields. The experimental results suggest that an encapsulation of the K cation by glymes as K(glyme)2 inhibits the contact between the K cation and the reactive anionic pentafluoroethyl counterion, preventing their transformation into KF and explosive tetrafluoroethylene (TFE). The generation