Autoxidation of Hydrocarbons: From Chemistry to Catalysis

This contribution summarizes our recent efforts to unravel the radical chemistry of autoxidations. Abstraction of the weakly bonded αH-atom of the primary hydroperoxide product by chain carrying peroxyl radicals is identified as the source of major end products such as alcohol and ketone/aldehyde. In the case of cyclohexane autoxidation, this reaction is even responsible for the majority of ring-opened by-products. In a second part, different approaches to autoxidation catalysis are discussed, ranging from transition metal ion catalysis to organocatalysis with immobilized N-hydroxyphthalimide.