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Air Oxidation Reaction: History
Please note this is an old version of this entry, which may differ significantly from the current revision.
Subjects: Chemistry, Organic
Contributor: Helena Kang

An air oxidation reaction is an oxidation in which molecular oxygen supplied as air functions as the terminal oxidant for an organic substrate. The substrate transfers reducing equivalents to O2 either directly or, more commonly, through a catalyst and redox mediator that cycle between oxidation states [1]. Depending on the mechanism, oxygen may be incorporated into the product or reduced to water or hydrogen peroxide while another reagent supplies the product oxygen atom. Catalytic aerobic alcohol oxidation, for example, couples substrate dehydrogenation to O2 reduction through metal and organic redox cycles [2]. The defining criterion is consumption of atmospheric oxygen as the stoichiometric electron acceptor; a reaction merely conducted in an open flask but oxidized by an unrelated reagent is not air oxidation. Autoxidation through radical chains and controlled catalytic aerobic oxidation both belong to the class, but they differ in initiation, propagation, selectivity, and the identity of oxygen-derived intermediates such as peroxyl radicals or metal–oxygen species.

  • air oxidation
  • molecular oxygen
  • aerobic catalysis
  • terminal oxidant

Catalysis and Oxidation Reactions • Catalysis • Chemical Engineering • Physical Sciences

References

  1. Shannon S. Stahl; Palladium Oxidase Catalysis: Selective Oxidation of Organic Chemicals by Direct Dioxygen‐Coupled Turnover. Angew. Chem. Int. Ed. 2004, 43, 3400-3420, 10.1002/anie.200300630.
  2. Bradford L. Ryland; Shannon S. Stahl; Practical Aerobic Oxidations of Alcohols and Amines with Homogeneous Copper/TEMPO and Related Catalyst Systems. Angew. Chem. Int. Ed. 2014, 53, 8824-8838, 10.1002/anie.201403110.
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