Rhodium-Catalyzed ortho-Selective Carbene C-H Insertion of Unprotected Phenols Directed by a Transient Oxonium Ylide Intermediate

ortho-Selective carbene C-H insertion of unprotected phenols is achieved with dimethyl diazomalonate under the catalysis of [Rh(COD)Cl](2). After the C-H insertion, subsequent cyclization and electrophilic addition of another carbene molecule affords tris-carboxylate-substituted 2-benzofuranones as the final reaction products. The enantioselective variant has been developed with the use of chiral diene ligands. Mechanistic experiments indicate that a transient oxonium ylide directing group might be responsible for the regiocontrol at the C-H activation step.