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

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

Journal

Journal of the American Chemical Society
ISSN: 0002-7863 , E-ISSN: 1520-5126

Output data

Year: 2025, Volume: 147, Number: 1, Pages: 965–977 Pages count : DOI: 10.1021/jacs.4c14062

Authors

Belyakova Yulia Yu. ¹ , Radulov Peter S. ¹ , Novikov Roman A. ¹ , Prolomov Ilya V. ^2,1 , Krivoshchapov Nikolai V. ¹ , Medvedev Michael G. ^1,3 , Yaremenko Ivan A. ¹ , Alabugin Igor V. ⁴ , Terent’ev Alexander O. ¹

Affiliations

1	N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., Moscow 119991, Russian Federation
2	Mendeleev University of Chemical Technology, Miusskaya Sq. 9, Moscow 125047, Russian Federation
3	National Research University Higher School of Economics, Moscow 101000, Russian Federation
4	Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States

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.

Belyakova Y.Y. , Radulov P.S. , Novikov R.A. , Prolomov I.V. , Krivoshchapov N.V. , Medvedev M.G. , Yaremenko I.A. , Alabugin I.V. , Terent’ev A.O.
FeCl2-Mediated Rearrangement of Aminoperoxides into Functionalized Tetrahydrofurans: Dynamic Non-innocence of O-Ligands at an Fe Center Coordinates a Radical Cascade
Journal of the American Chemical Society. 2025. V.147. N1. P.965–977. DOI: 10.1021/jacs.4c14062 WOS OpenAlex

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