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.