Recent advances in computational studies on Cu-catalyzed aerobic reactions: cooperation of copper catalysts and dioxygen.

O 2 , one of the ideal oxidants, suffers from low solubility, low oxidizability, low selectivity and a triplet ground state when applied in organic synthesis. Biomimetic copper catalysis has been demonstrated to be a powerful method for activating and transforming O 2 to conduct aerobic reactions for a long time. On the other hand, the structures of Cu-O 2 complexes are complex with diverse downstream reactions, whereas active copper intermediates were rarely identified by experimental methods, making the mechanisms of many Cu-catalyzed aerobic reactions far from clear. In this context, computational studies emerged as an effective alternative to mechanistic studies on Cu-catalyzed aerobic reactions. This review introduces the relevant computational studies since 2012, focusing on showing the cooperation of copper catalysts and O 2 in dehydrogenation, oxygenation and coupling reactions.