Copper-Mediated Nitrogen-Atom Migration into Saturated Carbocycles.

The conversion of carbocyclic rings into medicinally significant heterocycles represents a promising emerging strategy for molecular remodeling of pharmaceutical lead compounds. The selective activation and functionalization of C(sp3)-C(sp3) bonds, however, remains a formidable challenge for generalizing these methods to saturated rings. We report an operationally straightforward, one-step method for the formal insertion of nitrogen atoms into the skeletal cores of saturated carbocycles. This method leverages the underexplored ability of nitrogen-centered radical intermediates to trigger deconstructive β-scission events, and we have discovered a Cu(II) system that both generates nitrogen-centered radicals directly from sulfonamides and mediates the oxidative cyclization of the ring-opened organoradical intermediates. Given its broad functional group tolerance, scalability, and capacity for late-stage scaffold-hopping, this strategy establishes nitrogen-centered radical-mediated β-scission as a viable, general tool for the synthesis of nitrogen heterocycles by skeletal editing.