Electroreductive Cleavage of C(sp3)–N Bonds in Saturated N-Carbonyl-Heterocycles

Nitrogen-containing heterocycles are ubiquitous in biologically active molecules, pharmaceuticals, and natural products.¹ Ring-opening C–N bond cleavage provides a powerful route to stereodefined linear amines, but existing methods are generally restricted to strained small-ring systems or require harsh conditions and prefunctionalized substrates.² Recent radical-based approaches have expanded access to ring opening of cyclic amines but remain largely limited to five-membered rings or smaller.^3,4 Here, we report an electroreductive strategy that switches C–N bond cleavage from a radical to an ionic pathway, enabling efficient heterolytic ring opening of a broad range of unstrained cyclic amines. The method is applicable to pyrrolidines, piperidines, azepines, azocanes, and macrocyclic amines, and accommodates diverse N-carbonyl activating groups, including amides, thioamides, carbamates, and ureas. This electrochemically enabled reactivity switch significantly broadens substrate scope, ring-size compatibility, and functional-group tolerance.