Ruthenium-Catalyzed Rearrangement of Aldoximes to Primary Amides in Water

The rearrangement of aldoximes to primary amides has been studied using the readily available arene-ruthenium(II) complex [RuCl2(eta(6)-C6Me6){P(NMe2)(3)}] (5 mol %) as catalyst. Reactions proceeded cleanly in pure water at 100 degrees C without the assistance of any cocatalyst, affording the desired amides in high yields (70-90%) after short reaction times (1-7 h). The process was operative with both aromatic, heteroaromatic, alpha,beta-unsaturated, and aliphatic aldoximes and tolerated several functional groups. Reaction profiles and experiments using O-18-labeled water indicate that two different mechanisms are implicated in these transformations. In both of them, nitrile intermediates are initially formed by dehydration of the aldoximes. These intermediates are then hydrated to the corresponding amides by the action of a second molecule of aldoxime or water. A kinetic analysis of the rearrangement of benzaldoxime to benzamide is also discussed.