Synthesis of ω ‐Functionalized Carbonyls from Hydroperoxides and N‐Hydroxy Compounds: Mn‐Assisted Generation of N ‐Oxyl and C‐Radicals Followed by Their Cross‐Сoupling

Synthesis of ω ‐Functionalized Carbonyls from Hydroperoxides and N‐Hydroxy Compounds: Mn‐Assisted Generation of N ‐Oxyl and C‐Radicals Followed by Their Cross‐Сoupling Full article

Journal

Asian Journal of Organic Chemistry
ISSN: 2193-5815 , E-ISSN: 2193-5807

Output data

Year: 2026, Volume: 15, Number: 5, Article number : e70434, Pages count : DOI: 10.1002/ajoc.70434

Authors

Demina Arina A. ¹ , Fomenkov Dmitri I. ¹ , Budnikov Alexander S. ¹ , Sliguzova Darya Yu. ^2,1 , Karachev Damir D. ^2,1 , Polyanskaya Victoria I. ^2,1 , Yaremenko Ivan A. ^2,1 , Terent'ev Alexander O. ^2,1

Affiliations

1	N. D. Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russian Federation
2	D. I. Mendeleev University of Chemical Technology of Russia Moscow Russian Federation

The manganese-catalyzed method for the synthesis of ω-functionalized ketones and esters from alicyclic hydroperoxides and N-hydroxy compounds has been discovered. The disclosed transformation proceeds via Mn(II)/Mn(III) catalytic cycle, which fulfills two key functions: the selective reduction of hydroperoxides to alkoxy radicals and oxidation of N-hydroxy compounds to N-oxyl radicals. The generated alkoxy radicals undergo β-scission to form primary alkyl radicals (ω-C-centered radicals), which subsequently engage in cross-coupling with N-oxyl radicals. In most cases, this process affords two types of products: a C─O coupling product (major) and a C─N coupling product (minor) reflecting spin density localization within the N-oxyl radicals. Notably, the initial hydroperoxide serves a dual role, acting both as an oxidant for Mn(II) and as a precursor of the C-centered radicals, thereby significantly enhancing atom-economy. The developed approach is applicable to a broad range of hydroperoxides and N-hydroxy compounds and affords ω-functionalized compounds with overall yields of C─O and C─N coupling products up to 83%.

Demina A.A. , Fomenkov D.I. , Budnikov A.S. , Sliguzova D.Y. , Karachev D.D. , Polyanskaya V.I. , Yaremenko I.A. , Terent'ev A.O.
Synthesis of ω ‐Functionalized Carbonyls from Hydroperoxides and N‐Hydroxy Compounds: Mn‐Assisted Generation of N ‐Oxyl and C‐Radicals Followed by Their Cross‐Сoupling
Asian Journal of Organic Chemistry. 2026. V.15. N5. e70434 . DOI: 10.1002/ajoc.70434 WOS Scopus OpenAlex

Submitted:	Nov 28, 2025
Published online:	May 9, 2026

≡ Web of science:	WOS:001764967700001
≡ Scopus:	2-s2.0-105038362481
≡ OpenAlex:	W7160708075