A review. Although catalytic redns., cross-couplings, metathesis, and oxidn. of C=C double bonds are well established, the corresponding catalytic hydroxylations of C-H bonds in alkanes, arenes, or benzylic (allylic) positions, particularly with O2, the cheapest, \dqgreenest\dq, and most abundant oxidant, are severely lacking. Certainly, some promising examples in homogenous and heterogenous catalysis exist, as well as enzymes that can perform catalytic aerobic oxidns. on various substrates, but these have never achieved an industrial-scale, owing to a low space-time-yield and poor stability. This review illustrates recent advances in aerobic oxidn. catalysis by discussing selected examples, and aims to stimulate further exciting work in this area. Theor. work on catalyst precursors, resting states, and elementary steps, as well as model reactions complemented by spectroscopic studies provide detailed insight into the mol. mechanisms of oxidn. catalyzes and pave the way for preparative applications. However, O2 also poses a safety hazard, esp. when used for large scale reactions, therefore sophisticated methodologies have been developed to minimize these risks and to allow convenient transfer onto industrial scale. on SciFinder(R)

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