Mechanistic Studies into Metal-Catalyzed Aldoxime to Amide Rearrangements

The metal-catalyzed rearrangement of aldoximes into primary amides is a completely atom economical synthetic method for the preparation of one of the most important functional groups in chemistry. There have been several reports of various metals successfully catalyzing this reaction, however, there are conflicting views as to the mechanism involved. Herein we report new experimental evidence to support the mechanism and whether this is universal to all catalysts reported or metal specific. We also describe our further studies into the mechanism of the nickel-catalyzed acylation of amines with aldoximes.