Aerobic asymmetric oxygenation catalysis: a well forgotten… future?

Aerobic dioxygen, the cheapest oxidant with the highest active oxygen content, has so far remained underrepresented in selective, including stereoselective, oxidation catalysis. This article surveys the milestones in the area of catalytic asymmetric oxidations of organic molecules leading to formation of new C–O or X–O bonds, reported in the last decades. The existing catalyst systems are outlined, and technical as well as fundamental difficulties that hamper widespread adoption of dioxygen into asymmetric oxygenation catalysis are discussed.