Facile Cleavage of Activated Ketones: An Access to Thioethers via In Situ Generation of Anhydrides by Pummerer-Type Rearrangement.

Herein, we report an oxygen insertion in activated ketones from simple inorganic carbonates for the synthesis of symmetric aromatic anhydrides. For the first time, Li 2 CO 3 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.