Transition‐Metal‐Free Reactions of Amides by Tetrahedral Intermediates

Although conceptually intuitive, adding carbon nucleophiles to amides en route to carbonyls and amines remained elusive for long time, thereby eclipsing the innate potential in synthesis. In recent years, the barriers posed by the well-known amides inertness have been completely surmounted, and nowadays, chemists can assemble sophisticated frameworks starting from these widely available feedstocks. Reported herein are the logics – e.g. modification of the amide linkage and electrophilic amide activation inter alia – enabling the achievement of the breakthroughs with particular emphasis on the literature published in the past 15 years.