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It was found that, copper as a cheap metal, could well catalyze the dehydration reaction of aldoximes to organonitriles in nitrile solvent by using MnO 2 as the co-catalyst and PPh 3 as the ligand. In contrast, instead of organonitriles, the Cu-catalyzed reactions of the aldoximes in water led to amides, which were the products of the Beckmann rearrangements. These interesting selectivity-switchable reactions afford easy accesses to the related useful organic compounds and may be of bothdoi:10.6023/cjoc201805044 fatcat:nw2ldcrokraavcllw2ngqdocfi