Synthesis of β-ketophosphonates through aerobic copper(II)-mediated phosphorylation of enol acetates

Synthesis of β-ketophosphonates through aerobic copper(II)-mediated phosphorylation of enol acetates Full article

Journal

Beilstein Journal of Organic Chemistry
ISSN: 2195-951X , E-ISSN: 1860-5397

Output data

Year: 2025, Volume: 21, Pages: 1192-1200 Pages count : 9 DOI: 10.3762/bjoc.21.96

Authors

Budnikov Alexander S ¹ , Krylov Igor B ¹ , Monin Fedor K ^2,1 , Merkulova Valentina M ¹ , Ilovaisky Alexey I ¹ , Yan Liu ^3,4 , Yu Bing ³ , 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	M. V. Lomonosov Moscow State University, 1 Leninskie Gory, 119991 Moscow, Russian Federation.
3	College of Chemistry, Zhengzhou University, Zhengzhou 450001, China.
4	Henan International Joint Laboratory of Rare Earth Composite Material, College of Materials Engineering, Henan University of Engineering, Zhengzhou 451191, China.

Aerobic copper(II)-mediated phosphorylation of enol acetates with H-phosphonates leading to the formation of β-ketophosphonates was discovered. The proposed method is applicable to a wide range of H-phosphonates or phosphine oxides as PH-reagents and enol acetates. Unlike previous reports, which generally employed stoichiometric amounts of oxidants or more expensive transition metal catalysts, the present protocol employs only cheap copper sulfate pentahydrate as a catalyst under mild reaction conditions. The achieved phosphorylation proceeds via the formation of P-centered radicals produced by the oxidation of PH-reagents by copper(II)-containing species. Employing anhydrous CuSO4 instead of the pentahydrate led to a dramatic phosphorylation yield drop from 70 to <5%. It seems that the ligand environment of copper is very important for the effective reaction: other Cu(II) and Cu(I) salts, including halides, nitrate, tetrafluoroborate, or perchlorate, were much less effective or completely inert.

Budnikov A.S. , Krylov I.B. , Monin F.K. , Merkulova V.M. , Ilovaisky A.I. , Yan L. , Yu B. , Terent'ev A.O.
Synthesis of β-ketophosphonates through aerobic copper(II)-mediated phosphorylation of enol acetates
Beilstein Journal of Organic Chemistry. 2025. V.21. P.1192-1200. DOI: 10.3762/bjoc.21.96 WOS OpenAlex

Web of science:	WOS:001522376900002
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