Fenton Chemistry for Achmatowicz Rearrangement

Achmatowicz rearrangement (AchR) is a very important transformation for the synthesis of various heterocyclic building blocks and natural products. Here, the discovery of Fenton chemistry for AchR using a bifunctional catalyst (FeBr2 or CeBr3), which has environmental friendliness and a broad substrate scope at the same time has been reported. This method addresses the major limitation of conventional chemical (hazardous) and enzymatic (limited scope) methods. Mechanistic studies suggested that reactive brominating species (RBS) is the true catalyst for AchR and that Fenton chemistry [Fe/Ce (cat.) + H2O2 -> HO center dot/HOO center dot + H2O] is responsible for the oxidation of bromide into RBS. Importantly, this in situ RBS generation from M-Br-x-H2O2. under neutral conditions addresses the long-lasting problem of many haloperoxidase mimics that require a strong acidic additive/medium for bromide oxidation with H2O2, which creates opportunities for many other brominium-mediated organic reactions.

Automated summary

The Achmatowicz rearrangement is a significant transformation for the synthesis of various heterocyclic building blocks and natural products. The discovery of Fenton chemistry for AchR using a bifunctional catalyst has environmental friendliness and a broad substrate scope, addressing limitations of conventional chemical and enzymatic methods. Reactice brominating species (RBS) is found to be the true catalyst for AchR, and the in situ RBS generation from M-Br-x-H2O2 under neutral conditions solves the longstanding issue of acidic additives required for bromide oxidation with H2O2, creating opportunities for other bromine-mediated organic reactions.