α‐Oxamination of Amides via Electrophilic Activation

Abstract

Abstract This chapter presents the procedure for α‐oxamination of amides via electrophilic activation. Selective oxidation reactions are valuable transformations in organic synthesis. Particularly, the α‐keto amide functionality has observed a spike in popularity in the synthetic chemistry community in recent years. Amide activation using triflic anhydride is a distinctive synthetic approach employed by multiple research groups in order to transform amides via chemoselective cycloaddition or nucleophilic addition processes. Reductive cleavage conditions lead to the corresponding α‐hydroxy amides, thus positioning the tetramethylpiperidine moiety as a “protecting group” for the hydroxy function. The authors have previously developed a chemoselective oxidation of amides to α‐keto amides and α‐hydroxy amides. The utility of such an approach is showcased by further transformations of the oxyaminated amides into synthetically useful building blocks accessible employing commonly used reagents.