Criegee Intermediates in Autoxidation Reactions: Mechanistic Considerations

Products of Criegee intermediate (CI) chemistry were recently detected in radical chain autoxidation reactions involving β-hydroxyperoxy radicals. Here, we demonstrate by means of accurate G4 computations that direct scission of the latter to CIs and radical byproducts is thermodynamically highly unfavorable. Instead, the reaction becomes possible through a hydrogen abstraction reaction that could proceed by reversible formation of a dimeric tetroxide and a subsequent [1,6] hydrogen shift of the hydroxy hydrogen.