Efficient Aerobic Oxidation of Organic Molecules by Multistep Electron Transfer

This Minireview presents recent important homogenous aerobic oxidative reactions which are assisted by electron transfer mediators (ETMs). Compared with direct oxidation by molecular oxygen (O(2)), the use of a coupled catalyst system with ETMs leads to a lower overall energy barrier via stepwise electron transfer. This cooperative catalytic process significantly facilitates the transport of electrons from the reduced form of the substrate‐selective redox catalyst (SSRC(red)) to O(2), thereby increasing the efficiency of the aerobic oxidation. In this Minireview, we have summarized the advances accomplished in recent years in transition‐metal‐catalyzed as well as metal‐free aerobic oxidations of organic molecules in the presence of ETMs. In addition, the recent progress of photochemical and electrochemical oxidative functionalization using ETMs and O(2) as the terminal oxidant is also highlighted. Furthermore, the mechanisms of these transformations are showcased.