DFT study of the uncatalyzed dioxygenation of acireductone

Results of DFT calculations suggest that the uncatalyzed reaction between acireductone and dioxygen has a radical mechanism. In an initiation step, calculated to be thermo-neutral, acireductone is one-electron oxidized by dioxygen to a radical species. This radical intermediate reacts with triplet dioxygen forming a ketoacid radical and formate. In a spontaneous propagation step acireductone reduces the ketoacid radical to the ketoacid anion.