An Efficient Protocol for the Synthesis of Primary Amides via Rh-Catalyzed Rearrangement of Aldoximes

A system consisting of catalytic amounts of [Rh(CH2 = CH2)Cl](2)/PPh2Cy, and PhCl as the solvent efficiently catalyzes selective rearrangement of aldoximes to furnish various primary amides in moderate to good yields. Replacing the [Rh(CH2 = CH2)Cl](2) with Rh(NBD)(2)OTf enables the superior transformation to afford the amides with up to 99% yields. Attractive synthetic features associated with this methodology include absence of co-catalysts, broad functional group tolerance, good to excellent yields, low metal loadings, and operational convenience.