-Selective carbene C-H insertion of unprotected phenols is achieved with dimethyl diazomalonate under the catalysis of [Rh(COD)Cl]. 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.
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