Highly selective partial oxidation of methane to methyl trifluoroacetate

Homogeneous Oxidation of Alkanes by Electrophilic Late Transition Metals

“…Unfortunately, several attempts to expand the scope of this chemistry have been complicated by difficulties in reproducing these results. [20,22,25,95] The selective oxidation of methane and other lower alkanes by O 2 was observed by Sen and co-workers, who employed 5 % Pd/C and soluble copper(ii) salts in a mixture of trifluoroacetic acid and water. [96,97] Methanol is the primary product of methane oxidation.…”

“…[20] Importantly, the methyl ester product is stable to further oxidation under the reaction conditions. Addition of O 2 to the reaction results in a 400 % yield of CF 3 CO 2 CH 3 based on the cobalt(iii) oxidizing equivalents available, presumably reflecting reoxidation of Co II by O 2 .…”

Cu(OAc)2-catalyzed partial oxidation of methane to methyl trifluoroacetate in the liquid phase

“…Various catalyst systems have also been investigated for the partial oxidation of methane to oxygenates in the liquid phase. [1][2][3][4][5][6][7] Recently we reported that the vanadium-containing heteropolyacid catalyst systems gave high yields of methyl trifluoroacetate. 8 In continuing studies on C-H bond activation, we report here our new results on the partial oxidation of methane to methyl trifluoroacetate using a Cu(OAc) 2 catalyst in trifluoroacetic acid (TFA).…”

Hydroperoxide oxidation: unexpected C–C bond cleavage in branched alkanes and oxidation of molecular nitrogen

“…A similar relation between ketonization and hydroxylation reactions was observed in alkane oxidation with dioxygen catalyzed by Co II /Co III in a solution of CF 3 COOH; this reaction is supposed to include a oneelectron transfer from the hydrocarbon molecule to metal cation [19,20].…”