Selective Synthesis of Allylated Oxime Ethers and Nitrones Based on Palladium-Catalyzed Allylic Substitution of Oximes

The viability of oximes as nucleophiles in transition-metal-catalyzed allylic substitution was examined. The oxygen atom of oxime acted as a reactive nucleophile in the reaction of a π-allyl palladium complex. In the presence of Pd(PPh<sub>3</sub>)<sub>4</sub>, the allylic substitution of oximes with allylic carbonate afforded the linear O-allylated oxime ethers selectively without a base. In contrast, the palladium-catalyzed reaction with allylic acetate proceeded smoothly in the presence of K<sub>2</sub>CO<sub>3</sub> or Et<sub>2</sub>Zn as a base. Selective formation of nitrones was achieved by using palladium(II) catalyst. In the presence of Pd(cod)Cl<sub>2</sub>, the allylic substitution of oximes with allylic acetate afforded the N-allylated nitrones under solvent-free conditions, as a result of the reaction with the nitrogen atom of oximes.