Chemoselective Oxidations and Umpolung Reactivity of Amides

The amide functionnality is ubiquitous in organic molecules. However, the influence of the nitrogen makes it one of the most stable and least reactive carbonyl derivative. Herein, we exploited the ability of triflic anhydride to activate amides, and developped chemoselective oxidations of amides to α-keto and α-hydroxy amides, as well as a novel umpolung reactivity through a key enolonium intermediate.