Transition metal (TM)-catalyzed direct C-H amination on free and fused pyridines is challenging, while it is much easier for their N-oxide derivatives. Unfortunately, most TM-catalysis is commonly used for nondeoxyamination and often limited to specific N-oxide and amine substrates. We herein disclose a combination of a copper(I) catalyst and dppf for deoxygenated oxidative C-N coupling of azine N-oxides to realize facile aminations on their parent azines, wherein dppf plays a crucial role in the deoxygenation step in the catalytic cycle. Moreover, this protocol tolerates a wider variety of N-oxides and free alicyclic amines to promise broader application potential.
Wang et al. (2026) studied this question.