Intramolecular Palladium‐Catalyzed Aminocarboxylation of Olefins as a Direct Route to Bicyclic Oxazolidinones

An efficient, direct synthesis of oxazolidinones fused to six‐membered heterocyclic rings starting from carbamate‐protected aminoalkenes has been developed. This procedure is based on an oxidative palladium(II)‐catalyzed reaction performed in the presence of stoichiometric copper chloride, which is determinant to promote the formation of the bicyclic product and prevent the isolation of the monocyclic amination product. Oxazolidinone compounds arise from a domino aminocarboxylation process through the direct intervention of the carbamate oxygen after the initial palladium‐promoted transfer of the nitrogen atom on the CC double bond.