Synergistic activating effects of a strong Lewis acid (metal ion) and a strong Brønsted acid enable KMnO₄ to oxidize CH₄ at room temperature

The search for reagents that can oxidize methane (CH₄) under mild conditions has long been a challenge for chemists. In this work, we report the synergistic effects of a strong Lewis acid Sc(OTf)₃ and a strong Brønsted acid CF₃CO₂H (TFA) to activate KMnO₄ towards the oxidation of CH₄ at room temperature. KMnO₄ in the presence of 0.5-2 mol equiv. of Sc(OTf)₃ in TFA/TFAA (1 : 4 by vol., TFAA = trifluoroacetic anhydride) is able to oxidize CH₄ (30 atm) at 22 °C to produce methyl trifluoroacetate (CF₃CO₂CH₃) in 17 ± 2% yield (based on KMnO₄). The yield increases to 34% when the temperature is raised to 40 °C. No product is observed when using Sc(OTf)₃ alone, and only 2% of methyl trifluoroacetate is produced using TFA alone. A kinetic isotope effect of 2.2 is found when using a mixture of CH₄ and CD₄ as the substrate. The use of BrCCl₃ as a radical trap results in the formation of BrCH₃, indicating that the CH₃^• radical is an intermediate in CH₄ oxidation. These results suggest that Sc(OTf)₃ and TFA form an active intermediate with MnO₄^-, which undergoes hydrogen-atom abstraction (HAT) from CH₄ to produce CH₃^•, which is further oxidized to CH₃OH. Further oxidation of CH₃OH is prevented by its trapping with TFAA to produce CF₃CO₂CH₃. DFT calculations show that Sc(OTf)₂⁺ and CF₃CO₂H combine with MnO₄^- to produce an active intermediate that undergoes HAT with CH₄ with a low barrier of 12.5 kcal mol^-1. © the Partner Organisations 2025.