Synthesis of β-ketophosphonates through aerobic copper(II)-mediated phosphorylation of enol acetates
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 gen...
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| Format: | Article |
| Language: | English |
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Beilstein-Institut
2025-06-01
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| Series: | Beilstein Journal of Organic Chemistry |
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| Online Access: | https://doi.org/10.3762/bjoc.21.96 |
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| author | Alexander S. Budnikov Igor B. Krylov Fedor K. Monin Valentina M. Merkulova Alexey I. Ilovaisky Liu Yan Bing Yu Alexander O. Terent’ev |
| author_facet | Alexander S. Budnikov Igor B. Krylov Fedor K. Monin Valentina M. Merkulova Alexey I. Ilovaisky Liu Yan Bing Yu Alexander O. Terent’ev |
| author_sort | Alexander S. Budnikov |
| collection | DOAJ |
| description | 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. |
| format | Article |
| id | doaj-art-779e397a779c4a418d618fa8591ac683 |
| institution | Kabale University |
| issn | 1860-5397 |
| language | English |
| publishDate | 2025-06-01 |
| publisher | Beilstein-Institut |
| record_format | Article |
| series | Beilstein Journal of Organic Chemistry |
| spelling | doaj-art-779e397a779c4a418d618fa8591ac6832025-08-20T03:28:17ZengBeilstein-InstitutBeilstein Journal of Organic Chemistry1860-53972025-06-012111192120010.3762/bjoc.21.961860-5397-21-96Synthesis of β-ketophosphonates through aerobic copper(II)-mediated phosphorylation of enol acetatesAlexander S. Budnikov0Igor B. Krylov1Fedor K. Monin2Valentina M. Merkulova3Alexey I. Ilovaisky4Liu Yan5Bing Yu6Alexander O. Terent’ev7N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation College of Chemistry, Zhengzhou University, Zhengzhou 450001, China College of Chemistry, Zhengzhou University, Zhengzhou 450001, China N. D. Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences, 47 Leninsky prosp., 119991 Moscow, Russian Federation 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.https://doi.org/10.3762/bjoc.21.96c–p couplingcopperenol acetatesβ-ketophosphonatesphosphorylation |
| spellingShingle | Alexander S. Budnikov Igor B. Krylov Fedor K. Monin Valentina M. Merkulova Alexey I. Ilovaisky Liu Yan Bing Yu Alexander O. Terent’ev Synthesis of β-ketophosphonates through aerobic copper(II)-mediated phosphorylation of enol acetates Beilstein Journal of Organic Chemistry c–p coupling copper enol acetates β-ketophosphonates phosphorylation |
| title | Synthesis of β-ketophosphonates through aerobic copper(II)-mediated phosphorylation of enol acetates |
| title_full | Synthesis of β-ketophosphonates through aerobic copper(II)-mediated phosphorylation of enol acetates |
| title_fullStr | Synthesis of β-ketophosphonates through aerobic copper(II)-mediated phosphorylation of enol acetates |
| title_full_unstemmed | Synthesis of β-ketophosphonates through aerobic copper(II)-mediated phosphorylation of enol acetates |
| title_short | Synthesis of β-ketophosphonates through aerobic copper(II)-mediated phosphorylation of enol acetates |
| title_sort | synthesis of β ketophosphonates through aerobic copper ii mediated phosphorylation of enol acetates |
| topic | c–p coupling copper enol acetates β-ketophosphonates phosphorylation |
| url | https://doi.org/10.3762/bjoc.21.96 |
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