Selective Catalytic Oxidation of C-H Bonds with Molecular Oxygen

Publikations-Art

Zeitschriftenbeitrag (peer-reviewed)

Autoren

Roduner, E.; Kaim,W.; Sarkar, B.; Urlacher, V. B.; Pleiss, J.; Gläser R.; Einicke, W.-D.; Sprenger, G. A.; Beifuß, U.; Klemm, E.; Liebner, C.; Hieronymus, H.; Hsu, S.-F.; Plietker, B.; Laschat, S.

Erscheinungsjahr

2013

Veröffentlicht in

ChemCatChem

Band/Volume

5/

DOI

10.1002/cctc.201200266

Seite (von - bis)

82-112

Although catalytic reductions, cross-couplings, metathesis, and oxidation 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, “greenest”, 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 oxidations 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 oxidation catalysis by discussing selected examples, and aims to stimulate further exciting work in this area. Theoretical work on catalyst precursors, resting states, and elementary steps, as well as model reactions complemented by spectroscopic studies provide detailed insight into the molecular mechanisms of oxidation catalyses and pave the way for preparative applications.

However, O₂ also poses a safety hazard, especially when used for large scale reactions, therefore sophisticated methodologies have been developed to minimize these risks and to allow convenient transfer onto industrial scale.