Tailoring the Coordination Environment of Cu Single\nAtoms for Achieving Regioselective C–C Bond Activation of Amides

C–C\nbond activation can provide a direct reconstruction\nstrategy of carbon skeletons to furnish a number of structurally diverse\nmolecules. In general, regioselectivity represents the state-of-the-art\nowing to the existence of several different carbon–carbon bonds,\nhaving a high BDE, ∼90 kcal/mol. Here, we report a directed\nstrategy for amides for the concise synthesis of a range of urea derivatives\nand carbamates via regioselective C–C bond activation enabled\nby the heterogeneous single-atom copper catalyst (Cu-SAC), with a\nturnover frequency of 249 h<sup>–1</sup>, which is 19 times\nhigher than that of the analogous homogeneous copper catalyst. Multitechnique\ncharacterization data show that single-atom Cu species are associated\nwith an unsaturated coordination structure and plentiful oxygen vacancies\non γ-Al<sub>2</sub>O<sub>3</sub> that facilitate the adsorption\nof multiple coordinated amides and dioxygen, leading to high catalytic\nactivity and selectivity. It would offer opportunities to speed up\nthe heterogenized process of homogeneous catalysts in regioselective\ninert-bond activation reactions.