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

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posted on 2005-07-08, 00:00 authored by Hideto Miyabe, Kazumasa Yoshida, Valluru Krishna Reddy, Akira Matsumura, Yoshiji Takemoto
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(PPh3)4, 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 K2CO3 or Et2Zn as a base. Selective formation of nitrones was achieved by using palladium(II) catalyst. In the presence of Pd(cod)Cl2, 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.

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