FeCl<sub>2</sub>‑Mediated\nRearrangement of\nAminoperoxides into Functionalized Tetrahydrofurans: Dynamic Non-innocence\nof O‑Ligands at an Fe Center Coordinates a Radical Cascade

The selective reaction of cyclic aminoperoxides with\nFeCl<sub>2</sub> proceeds through a sequence of O–O and C–C\nbond cleavages,\nfollowed by intramolecular cyclization, yielding functionalized tetrahydrofurans\nin 44–82% yields. Replacing the peroxyacetal group in the peroxide\nstructure with a peroxyaminal fragment fundamentally alters the reaction\npathway. Instead of producing linear functionalized ketones, this\nmodification leads to the formation of hard-to-access substituted\ntetrahydrofurans. Although the aminoperoxide cores undergo multiple\nbond scissions, this cascade is atom-economical. Computational analysis\nshows that the O-ligands at the Fe center have enough radical character\nto promote C–C bond fragmentation and subsequent cyclization.\nThe stereoelectronic flexibility of oxygen, combined with iron’s\ncapacity to stabilize multiple reactive intermediates during the multistep\ncascade, explains the efficiency of this new atom-economic peroxide\nrearrangement.