Copper(I)-Catalyzed α,β-Dehydrogenative [2 + 3] Heteroannulation of Saturated Amines with Diaziridinone via Hydrogen Atom Transfer

The site-selective functionalization of carbon(sp³)–hydrogen bonds in saturated amines remains a persistent challenge owing to their intrinsic electronic deficiency, particularly in activating the α and β positions simultaneously for annulation reactions. Herein, we report a copper(I)-catalyzed dehydrogenation and [2 + 3] cycloaddition of commercially available amines with diaziridinone, which facilitated the direct synthesis of highly valuable imidazolidone derivatives. Operationally simple methodology has a broad substrate scope and convenient scalability, providing an effective and complementary platform for the rapid incorporation of N-heterocycles into amine molecules. Furthermore, comprehensive mechanistic investigations and computational studies indicated the pathway of the radical-type hydrogen atom transfer and [2 + 3] cycloaddition, which were promoted by a four-membered copper(III) species.