Redox‐Neutral Cu‐Catalyzed Cyclative γ‐C–H Functionalization Enroute to Aza‐ and Oxo‐heterocycles

Abstract Cyclative C(sp 3 )–H functionalization of unactivated C─H bonds with heteroatoms is a straightforward way to construct saturated aza‐ and oxo‐heterocycles, which continues to display ever‐increasing prevalence in drug design. Building upon our recently reported copper catalysis that used simple N ‐methoxyamides as radical precursors, we report a method to access diverse aza‐ and oxo‐heterocycles, including cyclic sulfonamides, cyclic ethers, and lactones of different ring sizes. By placing a heteroatom in the N ‐methoxyamide substrate, the carbon radical formed at the γ‐position from the intramolecular H‐abstraction by the amidyl radical could be trapped with the pendant heteroatom, leading to a redox‐neutral Cu‐catalyzed cyclative γ‐C(sp 3 )–H functionalization. The syntheses of a wide range of saturated aza‐ and oxo‐heterocycles demonstrate the versatility of this method.