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

• Alexander S. Budnikov,
• Igor B. Krylov,
• Fedor K. Monin,
• Valentina M. Merkulova,
• Alexey I. Ilovaisky,
• Liu Yan,
• Bing Yu and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2025, 21, 1192–1200, doi:10.3762/bjoc.21.96

• .21.96 Abstract 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

• ) salts, including halides, nitrate, tetrafluoroborate, or perchlorate, were much less effective or completely inert. Keywords: C–P coupling; copper; enol acetates; β-ketophosphonates; phosphorylation; Introduction The construction of C–P bonds is a highly important task in key areas of modern chemistry

• [1][2][3][4][5] due to the numerous applications of phosphorus-containing compounds in pharmaceuticals, biology, agrochemistry, organic synthesis, and materials science [6][7][8][9][10][11][12][13]. Among various organophosphorus compounds, β-ketophosphonates have received particular attention for

O,S,Se-containing Biginelli products based on cyclic β-ketosulfone and their postfunctionalization

• Kateryna V. Dil and
• Vitalii A. Palchykov

Beilstein J. Org. Chem. 2024, 20, 2143–2151, doi:10.3762/bjoc.20.184

• amides, coumarins, alicyclic ketones, β-ketophosphonates, α-nitroketones, curcumin, and barbituric acid derivatives [1][2][8][9]. We analyzed a number of Biginelli-type products and publications and concluded that Se-containing DHPMs among the rarest examples and, in addition to this, ketosulfones have

Multicomponent syntheses of pyrazoles via (3 + 2)-cyclocondensation and (3 + 2)-cycloaddition key steps

• Ignaz Betcke,
• Alissa C. Götzinger,
• Maryna M. Kornet and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2024, 20, 2024–2077, doi:10.3762/bjoc.20.178

Recent advances in transition-metal-catalyzed incorporation of fluorine-containing groups

• Xiaowei Li,
• Xiaolin Shi,
• Xiangqian Li and
• Dayong Shi

Beilstein J. Org. Chem. 2019, 15, 2213–2270, doi:10.3762/bjoc.15.218

• approach could be extended to asymmetric gem-chlorofluorination of β-ketophosphonates. Two years later, the same authors [72] demonstrated the highly enantioselective fluorination of α-alkyl-β-keto esters and α-alkylmalonates using the same catalyst system (Scheme 29b). Moreover, various cyclic and acyclic

Synthesis of 1-indanones with a broad range of biological activity

• Marika Turek,
• Dorota Szczęsna,
• Marek Koprowski and
• Piotr Bałczewski

Beilstein J. Org. Chem. 2017, 13, 451–494, doi:10.3762/bjoc.13.48

• Knoevenagel olefinations, followed by a Nazarov cyclization using FeCl3 or AlCl3. The 2-phosphorylated chalcones (Z)-145 and non-phosphorylated ones (E)-146 could be obtained from the same substrates, β-ketophosphonates 143 and aromatic aldehydes 144 depending on the reaction conditions used (piperidine

Multicomponent reactions: A simple and efficient route to heterocyclic phosphonates

• Mohammad Haji

Beilstein J. Org. Chem. 2016, 12, 1269–1301, doi:10.3762/bjoc.12.121

• carbonyl compounds such as β-diketones, β-keto thioesters, acetoacetamides and nitroacetone have been shown to participate in the classical Biginelli reaction [25], β-ketophosphonates 6 were found to be unreactive in similar conditions [26]. However, Yuan et al. developed a modified Biginelli condensation

• the electrophilic double bond of the CF3−C=N segment (Scheme 4). Idris Essid and Soufiane Touil showed that the Biginelli condensation of β-ketophosphonates was highly sensitive to the nature of solvents, acid catalysts and reactants [28]. They found that the use of inorganic acids including HCl and

• peptidomimetics possessing phosphonate groups by MCR-based strategies would significantly extend the synthetic potential of MCRs towards heterocyclic phosphonates. The Biginelli condensation. The Biginelli reaction of β-ketophosphonates catalyzed by ytterbium triflate. Trimethylchlorosilane-mediated Biginelli