The rearrangement of aldoximes to primary amides has been studied using the readily available arene-ruthenium (II) complex [RuCl2 (η6-C6Me6){P (NMe2) 3}](5 mol%) as catalyst. Reactions proceeded cleanly in pure water at 100° 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, α, β-unsaturated, and ...