Herein, we report an oxygen insertion in activated ketones from simple inorganic carbonates for the synthesis of symmetric aromatic anhydrides. For the first time, Li2CO3 acts as an oxygen source and the in situ generated symmetric aromatic anhydrides undergo Pummerer-type rearrangement to access α-benzoyloxy-thioethers. Attractively, this protocol occurs under metal-, ligand-, and oxidant-free conditions and is compatible with a wide range of substrates. Control experiments reveal the reaction pathway.