Synthesis of ω-functionalized ketones from strained cyclic alcohols by ring-opening and cross-recombination between alkyl and N-oxyl radicals

Synthesis of ω-functionalized ketones from strained cyclic alcohols by ring-opening and cross-recombination between alkyl and N-oxyl radicals Full article

Journal

Organic and Biomolecular Chemistry
ISSN: 1477-0520 , E-ISSN: 1477-0539

Output data

Year: 2024, Volume: 22, Pages: 8755-8763 Pages count : 9 DOI: 10.1039/d4ob01490a

Authors

Budnikov Alexander S ¹ , Krylov Igor B ¹ , Shevchenko Mikhail I ¹ , Sokova Lyubov' L ¹ , Liu Yan ^2,3 , Yu Bing ² , Terent'ev Alexander O ¹

Affiliations

1	N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation.
2	College of Chemistry, Zhengzhou University, Zhengzhou 450001, China.
3	Henan International Joint Laboratory of Rare Earth Composite Material, College of Materials Engineering, Henan University of Engineering, Zhengzhou 451191, China.

Radical ring-opening oxyimidation of cyclobutanols and cyclopropanols with the formation of ω-functionalized ketones was discovered. The oxidative C–O coupling proceeds via the interception of a primary alkyl radical generated from a cyclic alcohol with a reactive radical generated in situ, which is an electron-deficient N-oxyl radical. The developed conditions allow for the balanced generation rates of carbon- and N-oxyl radicals, which are necessary for their selective cross-recombination. Thus, typical competitive dimerization processes of carbon-centered radicals, their intermolecular cyclization, and N-oxyl radical self-decay are suppressed. The method is applicable to a wide range of cyclobutanols and results in oxyimidated ketones in yields of up to 82%.

Budnikov A.S. , Krylov I.B. , Shevchenko M.I. , Sokova L.L. , Liu Y. , Yu B. , Terent'ev A.O.
Synthesis of ω-functionalized ketones from strained cyclic alcohols by ring-opening and cross-recombination between alkyl and N-oxyl radicals
Organic and Biomolecular Chemistry. 2024. V.22. P.8755-8763. DOI: 10.1039/d4ob01490a WOS OpenAlex

Web of science:	WOS:001335740000001
OpenAlex:	W4403069897

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