Tuning the donor ability of oxygen with the inverse α-effect: two levels of kinetic control open access to four classes of peroxygenated heterocycles

Tuning the donor ability of oxygen with the inverse α-effect: two levels of kinetic control open access to four classes of peroxygenated heterocycles Full article

Journal

Organic Chemistry Frontiers
ISSN: 2052-4110 , E-ISSN: 2052-4129

Output data

Year: 2026, DOI: 10.1039/d6qo00028b

Authors

Skokova Ksenia V. ¹ , Belyakova Yulia Yu. ¹ , Radulov Peter S. ¹ , Fomenkov Dmitri I. ¹ , Krylov Igor B. ¹ , Yaremenko Ivan A. ¹ , Alabugin Igor V. ² , 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	Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Fl 32306, USA

A tunable acid-catalyzed reaction with hydrogen peroxide opens access to diverse oxygen-rich cyclic peroxides from common 1,4-diketone precursors. Precise kinetic control via acid and hydrogen peroxide loadings selectively channels the reaction along distinct mechanistic pathways, leading to ozonides, tetraoxanes, 1,2-dioxanes, or dihydroperoxyfurans, all obtained in good yields. The gatekeepers of these pathways are key cationic intermediates, with stereoelectronic effects playing a central role in determining product distribution. This mechanistic feature offers a versatile route to structurally diverse peroxides from a single precursor.

Skokova K.V. , Belyakova Y.Y. , Radulov P.S. , Fomenkov D.I. , Krylov I.B. , Yaremenko I.A. , Alabugin I.V. , Terent'ev A.O.
Tuning the donor ability of oxygen with the inverse α-effect: two levels of kinetic control open access to four classes of peroxygenated heterocycles
Organic Chemistry Frontiers. 2026. DOI: 10.1039/d6qo00028b WOS Scopus OpenAlex

Submitted:	Jan 9, 2026
Published print:	Mar 16, 2026

≡ Web of science:	WOS:001729224300001
≡ Scopus:	2-s2.0-105034435172
≡ OpenAlex:	W7137033572