FeCl₂-Mediated Rearrangement of Aminoperoxides into Functionalized Tetrahydrofurans: Dynamic Non-innocence of O-Ligands at an Fe Center Coordinates a Radical Cascade

The selective reaction of cyclic aminoperoxides with FeCl₂ proceeds through a sequence of O-O and C-C bond cleavages, followed by intramolecular cyclization, yielding functionalized tetrahydrofurans in 44-82% yields. Replacing the peroxyacetal group in the peroxide structure with a peroxyaminal fragment fundamentally alters the reaction pathway. Instead of producing linear functionalized ketones, this modification leads to the formation of hard-to-access substituted tetrahydrofurans. Although the aminoperoxide cores undergo multiple bond scissions, this cascade is atom-economical. Computational analysis shows that the O-ligands at the Fe center have enough radical character to promote C-C bond fragmentation and subsequent cyclization. The stereoelectronic flexibility of oxygen, combined with iron's capacity to stabilize multiple reactive intermediates during the multistep cascade, explains the efficiency of this new atom-economic peroxide rearrangement.