Anomeric amides are a unique class of molecules that can perform a variety of functions in synthesis. To empower future discovery of anomeric amide reagents and their reactions, it is imperative to understand the existing transformations as much as possible. This thesis is based in trying to uncover and distinguish differences in reactivity of anomeric amides and their reaction partners to enhance our understanding of how these reagents can be best manipulated and put safely into practice in synthetic chemistry. Chapter one reviews the applications of anomeric amide reagents, with a focus on modern developments within synthetic chemistry. Chapter two covers investigations of structure-reactivity relationships in N-(benzyloxy)-N-(pivaloyloxy)benzamides. These include kinetic reaction monitoring, linear free energy relationships, and DFT computed parameters to improve our knowledge of the structural features that influence the reactivity of these reagents within the context of secondary amine deletion. Chapter 3 looks instead at the impact of the amine’s structure on the reaction mechanism. The discovery and scope of primary amine deletion is briefly discussed, while the chapter’s focus is on the mechanistic experiments that were used to elucidate the radical-chain mechanism that accounts for the drastically different reactivity requirements observed for these substrates. Chapter 4 discusses optimization efforts and safety considerations in scaling a primary amine deletion, as these can be a useful transformation for transforming readily available amine feedstocks. The Appendix ventures away from nitrogen deletion and anomeric amides to share a story of a failed decarbonylation strategy that took on a new life within a tandem nitrene-internalization carbon-deletion reaction that transforms aryl azides into pyridines through removal of the ipso-carbon.