期刊
CHEMCATCHEM
卷 5, 期 1, 页码 82-112出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cctc.201200266
关键词
coupling reactions; feedstocks; hydroxylation; molecular oxygen; oxidation
资金
- Deutsche Forschungsgemeinschaft [SFB 706, INST 41/815-1]
- Ministerium fur Wissenschaft, Forschung und Kunst des Landes Baden-Wurttemberg
- Fonds der Chemischen Industrie
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 O-2, 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, O-2 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.
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