Application of diethyl ethynephosphonate for the synthesis of 3-phosphonylated β-lactams via Kinugasa reaction

Obijalska, Emilia; Kowalski, Marcin; Mlostoń, Grzegorz; Heimgartner, Heinz

doi:10.3998/ark.5550190.p009.660

Cited by 3 publications

(4 citation statements)

References 19 publications

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“…This is, to the best of our knowledge, the first example of PPh 3 synthesis without the involvement of P 4 . There are many established procedures that convert 2b into other useful organophosphorus compounds as well. − Moreover, ethynyl phosphonate offers opportunities for terminal phosphate modification of bioactive molecules. Nucleoside tetraphosphate 4 featuring a “clickable” moiety, for example, can be readily synthesized from the TBA salt 2′ using a diphosphorylation protocol recently developed by our group (Figure B) .…”

Section: Resultsmentioning

confidence: 99%

Mechanochemical Phosphorylation of Acetylides Using Condensed Phosphates: A Sustainable Route to Alkynyl Phosphonates

Xin

Cummins

2023

ACS Cent. Sci.

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In pursuit of a more sustainable route to phosphorus−carbon (P−C) bond-containing chemicals, we herein report that phosphonates can be prepared by mechanochemical phosphorylation of acetylides using polyphosphates in a single step, redoxneutral process, bypassing white phosphorus (P 4 ) and other high-energy, environmentally hazardous intermediates. Using sodium triphosphate (Na 5 P 3 O 10 ) and acetylides, alkynyl phosphonates 1 can be isolated in yields of up to 32%, while reaction of sodium pyrophosphate (Na 4 P 2 O 7 ) and sodium carbide (Na 2 C 2 ) engendered, in an optimized yield of 63%, ethynyl phosphonate 2, an easily isolable compound that can be readily converted to useful organophosphorus chemicals. Highly condensed phosphates like Graham's salt and bioproduced polyphosphate were also found to be compatible after reducing the chain length by grinding with orthophosphate. These results demonstrate the possibility of accessing organophosphorus chemicals directly from condensed phosphates and may offer an opportunity to move toward a "greener" phosphorus industry.

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Section: Resultsmentioning

confidence: 99%

Mechanochemical Phosphorylation of Acetylides Using Condensed Phosphates: A Sustainable Route to Alkynyl Phosphonates

Xin

Cummins

2023

ACS Cent. Sci.

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“…This was done for the first time by Kowalski and coworkers using diethyl ethynylphosphonate (119), a compound which is more often studied for its application in [3 + 2] cycloadditions with azides (Scheme 25). 127 An initial experiment performed by the group, between N-benzyl-phenyl nitrone (120) and 119 in anhydrous acetonitrile and under an inert atmosphere, catalyzed by copper iodide and triethylamine, yielded the desired product (123). Proton NMR analysis revealed that the product was obtained exclusively in the trans configuration.…”

Section: -Phosphono β-Lactamsmentioning

confidence: 99%

“…The compound itself is initially formed in the cis form, after which it spontaneously isomerizes because of the basic conditions of the reaction mixture. and 2-acetyl-1-pyrroline (127). Pyrrolidinone derivatives, such as oxiracetam (128), are well-known for their bioactivity that include respiratory stimulation and anticonvulsant activity (Figure 6).…”

Section: -Phosphono β-Lactamsmentioning

confidence: 99%

Synthetic Methods for Azaheterocyclic Phosphonates and Their Biological Activity: An Update 2004–2024

Mayorquín-Torres,

Simoens,

Bonneure

et al. 2024

Chem. Rev.

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The increasing importance of azaheterocyclic phosphonates in the agrochemical, synthetic, and medicinal field has provoked an intense search in the development of synthetic routes for obtaining novel members of this family of compounds. This updated review covers methodologies established since 2004, focusing on the synthesis of azaheterocyclic phosphonates, of which the phosphonate moiety is directly substituted onto to the azaheterocyclic structure. Emphasizing recent advances, this review classifies newly developed synthetic approaches according to the ring size and providing information on biological activities whenever available. Furthermore, this review summarizes information on various methods for the formation of C–P bonds, examining sustainable approaches such as the Michaelis–Arbuzov reaction, the Michaelis–Becker reaction, the Pudovik reaction, the Hirao coupling, and the Kabachnik–Fields reaction. After analyzing the biological activities and applications of azaheterocyclic phosphonates investigated in recent years, a predominant focus on the evaluation of these compounds as anticancer agents is evident. Furthermore, emerging applications underline the versatility and potential of these compounds, highlighting the need for continued research on synthetic methods to expand this interesting family.

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“…Substituted dienes [28], furane [29], anthracene derivatives [30] and pyrones [31,32] were applied as diene components, and azides [33], nitrile oxides [34] and diazomethane [27] were used as 1,3-dipoles. Dialkyl ethynylphosphonates are also effective dipolarophiles and are often used for the construction of triazole [35,36], pyrazole [37,38] and β-lactam [39] units. However, only several examples of cycloaddition reactions of 2-substituted ethynylphosphonates bearing aryl-, alkyl-or sulfonamide substituent with azides [40,41] or nitrile oxides [42,43] have been reported recently.…”

Section: Introductionmentioning

confidence: 99%

Oxidative [3+2]Cycloaddition of Alkynylphosphonates with Heterocyclic N-Imines: Synthesis of Pyrazolo[1,5-a]Pyridine-3-phosphonates

et al. 2022

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A series of pyrazolo[1,5-a]pyridine-3-ylphosphonates were prepared with moderate to good yields by the oxidative [3+2]cycloaddition of 2-subtituted ethynylphosphonates with in situ generated pyridinium-N-imines and their annulated analogs. 2-Aliphatic and 2-Ph acetylenes demonstrate low activity, and the corresponding pyrazolopyridines were achieved with a moderate yield in the presence of 10 mol% Fe(NO3)3·9H2O. At the same time, tetraethyl ethynylbisphosphonate, diethyl 2-TMS- and 2-OPh-ethynylphosphonates possess much greater reactivity and the corresponding pyrazolo[1,5-a]pyridines, and their annulated derivatives were obtained with good to excellent yields without any catalyst. 2-Halogenated ethynylphosphonates also readily reacted with pyridinium-N-imines, forming complex mixtures containing poor amounts of 2-halogenated pyrazolopyridines.

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Application of diethyl ethynephosphonate for the synthesis of 3-phosphonylated β-lactams via Kinugasa reaction

Cited by 3 publications

References 19 publications

Mechanochemical Phosphorylation of Acetylides Using Condensed Phosphates: A Sustainable Route to Alkynyl Phosphonates

Mechanochemical Phosphorylation of Acetylides Using Condensed Phosphates: A Sustainable Route to Alkynyl Phosphonates

Synthetic Methods for Azaheterocyclic Phosphonates and Their Biological Activity: An Update 2004–2024

Oxidative [3+2]Cycloaddition of Alkynylphosphonates with Heterocyclic N-Imines: Synthesis of Pyrazolo[1,5-a]Pyridine-3-phosphonates

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