Skeletal Rearrangements of Amides via Breaking Inert Bonds

Skeletal rearrangements of amides provide a rapid access to complex nitrogen‐containing scaffolds from simple readily available starting materials. While classical reactions such as the Hofmann and Curtius rearrangements have been widely utilized in organic synthesis, recent advances in amide activation strategies have brought new types of transformations and offered many new applications. This review focuses on the development of amide skeletal rearrangement reactions over the past two decades. The content is organized based on the initial bond cleavage pathways: C–N bond cleavage, C–C bond cleavage, and C=O bond activation.