scholarly journals Selective Esterification of Phosphonic Acids

Molecules ◽  
2021 ◽  
Vol 26 (18) ◽  
pp. 5637
Author(s):  
Damian Trzepizur ◽  
Anna Brodzka ◽  
Dominik Koszelewski ◽  
Ryszard Ostaszewski
Keyword(s):  
Reaction Mechanism ◽  
Phosphonic Acid ◽  
Large Scale ◽  
31P Nmr ◽  
Significant Loss ◽  
Alkoxy Group ◽  
Reaction Yield ◽  
31P Nmr Spectroscopy ◽  
Phosphonic Acids ◽  
Insight Into

Here, we report straightforward and selective synthetic procedures for mono- and diesterification of phosphonic acids. A series of alkoxy group donors were studied and triethyl orthoacetate was found to be the best reagent as well as a solvent for the performed transformations. An important temperature effect on the reaction course was discovered. Depending on the reaction temperature, mono- or diethyl esters of phosphonic acid were obtained exclusively with decent yields. The substrate scope of the proposed methodology was verified on aromatic as well as aliphatic phosphonic acids. The designed method can be successfully applied for small- and large-scale experiments without significant loss of selectivity or reaction yield. Several devoted experiments were performed to give insight into the reaction mechanism. At 30 °C, monoesters are formed via an intermediate (1,1-diethoxyethyl ester of phosphonic acid). At higher temperatures, similar intermediate forms give diesters or stable and detectable pyrophosphonates which were also consumed to give diesters. 31P NMR spectroscopy was used to assign the structure of pyrophosphonate as well as to monitor the reaction course. No need for additional reagents and good accessibility and straightforward purification are the important aspects of the developed protocols.

scholarly journals Direct determination of enantiomeric enrichment of chiral, underivatized aminophosphonic acids — useful for enantioselective bioconversion results evaluation

2013 ◽  
Vol 11 (9) ◽  
pp. 1542-1547
Author(s):  
Kinga Kozyra ◽  
Magdalena Klimek-Ochab ◽  
Małgorzata Brzezińska-Rodak ◽  
Ewa Żymańczyk-Duda
Keyword(s):  
31P Nmr ◽  
Enantiomeric Excess ◽  
Direct Determination ◽  
Shift Reagent ◽  
Racemic Mixture ◽  
31P Nmr Spectroscopy ◽  
Phosphonic Acids ◽  
Aminophosphonic Acids ◽  
Chiral Solvating Agent

AbstractAbstract The possibility of applying 31P NMR spectroscopy for the determination of the enantiomeric excess of the racemic mixture of non-derivatized aminophosphonic acids with small side chains has been investigated. It is proven, that the effectiveness of the application of a chiral solvating agent strongly depends on the concentration of applied shift reagent and on the pH of the particular experiment. Effectual resolution protocols are elaborated for following phosphonic acids: 1-aminoethanephosphonic acid, 1-amino-2-methylpropanephosphonic acid, 1-aminophenylmethanephosphonic acid, 1-aminophenylmethane-phosphonic acid and 1-amino-2-phenylethanephosphonic acid. Graphical abstract

scholarly journals A Pipeline for Making 31P NMR Accessible for Small- and Large-Scale Lipidomics Studies

2021 ◽  
Author(s):  
Samuel Furse ◽  
Huw Williams ◽  
Adam Watkins ◽  
Samuel Virtue ◽  
Antonio Vidal-Puig ◽  
...  
Keyword(s):  
Large Scale ◽  
31P Nmr ◽  
A Priori ◽  
Structural Data ◽  
Mass Spectrometry Data ◽  
Head Group ◽  
Sample Extraction ◽  
Tools And Techniques ◽  
Scientific Questions ◽  
Insight Into

Detailed molecular analysis is of increasing importance in research into the regulation of biochemical pathways, organismal growth and disease. Lipidomics in particular is increasingly sought after as it provides insight into molecular species involved in energy storage, signalling and fundamental cellular structures. This has led to the use of a range of tools and techniques to acquire lipidomics data. 31P NMR for lipidomics offers well-resolved head group/lipid class analysis, structural data that can be used to inform and strengthen interpretation of mass spectrometry data and part of structural determination a priori. In the present study, we codify the use of 31P NMR for lipidomics to make the technique more accessible to new users and more useful for a wider range of studies. We describe the process from sample extraction to data processing and analysis. This pipeline is important because it allows greater thoroughness in lipidomics studies and increases scope for answering scientific questions about lipid systems.

Synthesis and characterization of chiral aza-macrocycles and study of their enantiomer recognition ability for organo-phosphoric acid and phosphonic acid derivatives by 31P NMR and fluorescence spectroscopy

2016 ◽  
Vol 14 (9) ◽  
pp. 2742-2748 ◽  
Author(s):  
Aditya N. Khanvilkar ◽  
Ashutosh V. Bedekar
Keyword(s):  
Fluorescence Spectroscopy ◽  
Phosphoric Acid ◽  
Phosphonic Acid ◽  
31P Nmr ◽  
Optically Active ◽  
Chiral Discrimination ◽  
Synthesis And Characterization ◽  
Phosphonic Acids ◽  
Recognition Ability

Two diastereomers of optically active N,O-containing new macrocycles with dual chirality were synthesized and evaluated for chiral discrimination of organo phosphoric and phosphonic acids by 31P NMR and fluorescence spectroscopy.

Inhibition of Plasma Cholinesterase by O-Alkylfluorophosphonates

1997 ◽  
Vol 62 (3) ◽  
pp. 521-526 ◽  
Author(s):  
Jiří Cabal ◽  
Jiří Kassa ◽  
Jiří Patočka
Keyword(s):  
Kinetic Parameters ◽  
Phosphonic Acid ◽  
Methyl Esters ◽  
Plasma Cholinesterase ◽  
Alkoxy Group ◽  
Phosphonic Acids

Inhibition of plasma cholinesterase by three methylfluorophosphonates (MFF), sarin, soman and cyclosin, and by the products of their hydrolysis and alcoholysis was examined. Inhibition by phosphonic acids and by methyl esters derived from MFF was purely competitive while that by MFF was irreversible. The rate of phosphorylation of cholinesterase by MFF differs, depending on the structure of the alkoxy group in the MFF and decreases in the sequence soman-sarin-cyclosin. The affinity values of MFF, phosphonic acids and methyl esters of phosphonic acid for cholinesterase are comparable. The in vitro kinetic parameters suggest that plasma cholinesterase might act as a natural detoxicating agent in cases of poisoning with the above inhibitors of acetylcholinesterase.

scholarly journals Identification of transient intermediates in the bisphosphatase reaction of rat liver 6-phosphofructo-2-kinase/fructose-2,6-bisphosphatase by 31P-NMR spectroscopy

1995 ◽  
Vol 308 (1) ◽  
pp. 189-195 ◽  
Author(s):  
D A Okar ◽  
L T Kakalis ◽  
S S Narula ◽  
I M Armitage ◽  
S J Pilkis
Keyword(s):  
Reaction Mechanism ◽  
Nmr Spectroscopy ◽  
31P Nmr ◽  
Magnetization Transfer ◽  
Direct Analysis ◽  
Phosphoryl Group ◽  
31P Nmr Spectroscopy ◽  
Multiple Quantum ◽  
Depth Analysis ◽  
Field Shift

31P-NMR spectroscopy was used to identify reaction intermediates during catalytic turn-over of the fructose-2,6-bisphosphatase domain (Fru-2,6-P2ase) of the bifunctional enzyme, 6-phosphofructo-2-kinase/fructose-2,6-bisphosphatase. When fructose-2,6-bisphosphate (Fru-2,6-P2) was added to the enzyme, the 31P-NMR spectrum showed three resonances in addition to those of free substrate: the phosphohistidine (His-P) intermediate, the C-6 phosphoryl group of fructose-6-phosphate bound to the phosphoenzyme, and phosphate generated by the hydrolysis of substrate. Direct analysis of the alkali-denatured phospho-enzyme intermediate by 1H-31P heteronuclear multiple quantum-filtered coherence spectroscopy confirmed the formation of 3-N-phosphohistidine. Binding of fructose 6-phosphate to the bisphosphatase was detected by a down-field shift and broadening of the C-6 phosphoryl resonance. The down-field shift was greater in the presence of the phosphoenzyme intermediate. Inhibition of Fru-2,6-P2 hydrolysis by fructose 6-phosphate and Fru-2,6-P2 was shown to involve binding of the sugar phosphates to the phosphoenzyme. This study provides new experimental evidence in support of the reaction mechanism of Fru-2,6-P2ase and suggests that the steady-state His-P intermediate exists primarily in the E-P.fructose 6-phosphate complex. These results lay a solid foundation for the use of 31P-NMR magnetization transfer studies to provide an in-depth analysis of the bisphosphatase reaction mechanism.

scholarly journals Discovery of phosphonic acid natural products by mining the genomes of 10,000 actinomycetes

2015 ◽  
Vol 112 (39) ◽  
pp. 12175-12180 ◽  
Author(s):  
Kou-San Ju ◽  
Jiangtao Gao ◽  
James R. Doroghazi ◽  
Kwo-Kwang A. Wang ◽  
Christopher J. Thibodeaux ◽  
...  
Keyword(s):  
Natural Products ◽  
Phosphonic Acid ◽  
Large Scale ◽  
Genome Mining ◽  
Gene Clusters ◽  
High Rate ◽  
Phosphonic Acids ◽  
Strain Collection ◽  
Gene Level ◽  
Products Analysis

Although natural products have been a particularly rich source of human medicines, activity-based screening results in a very high rate of rediscovery of known molecules. Based on the large number of natural product biosynthetic genes in microbial genomes, many have proposed “genome mining” as an alternative approach for discovery efforts; however, this idea has yet to be performed experimentally on a large scale. Here, we demonstrate the feasibility of large-scale, high-throughput genome mining by screening a collection of over 10,000 actinomycetes for the genetic potential to make phosphonic acids, a class of natural products with diverse and useful bioactivities. Genome sequencing identified a diverse collection of phosphonate biosynthetic gene clusters within 278 strains. These clusters were classified into 64 distinct groups, of which 55 are likely to direct the synthesis of unknown compounds. Characterization of strains within five of these groups resulted in the discovery of a new archetypical pathway for phosphonate biosynthesis, the first (to our knowledge) dedicated pathway for H-phosphinates, and 11 previously undescribed phosphonic acid natural products. Among these compounds are argolaphos, a broad-spectrum antibacterial phosphonopeptide composed of aminomethylphosphonate in peptide linkage to a rare amino acid N5-hydroxyarginine; valinophos, an N-acetyl l-Val ester of 2,3-dihydroxypropylphosphonate; and phosphonocystoximate, an unusual thiohydroximate-containing molecule representing a new chemotype of sulfur-containing phosphonate natural products. Analysis of the genome sequences from the remaining strains suggests that the majority of the phosphonate biosynthetic repertoire of Actinobacteria has been captured at the gene level. This dereplicated strain collection now provides a reservoir of numerous, as yet undiscovered, phosphonate natural products.

scholarly journals A Pipeline for Making 31P NMR Accessible for Small- and Large-Scale Lipidomics Studies

2021 ◽  
Author(s):  
Samuel Furse ◽  
Huw Williams ◽  
Adam Watkins ◽  
Samuel Virtue ◽  
Antonio Vidal-Puig ◽  
...  
Keyword(s):  
Large Scale ◽  
31P Nmr ◽  
A Priori ◽  
Structural Data ◽  
Mass Spectrometry Data ◽  
Head Group ◽  
Sample Extraction ◽  
Tools And Techniques ◽  
Scientific Questions ◽  
Insight Into

Detailed molecular analysis is of increasing importance in research into the regulation of biochemical pathways, organismal growth and disease. Lipidomics in particular is increasingly sought after as it provides insight into molecular species involved in energy storage, signalling and fundamental cellular structures. This has led to the use of a range of tools and techniques to acquire lipidomics data. 31P NMR for lipidomics offers well-resolved head group/lipid class analysis, structural data that can be used to inform and strengthen interpretation of mass spectrometry data and part of structural determination a priori. In the present study, we codify the use of 31P NMR for lipidomics to make the technique more accessible to new users and more useful for a wider range of studies. We describe the process from sample extraction to data processing and analysis. This pipeline is important because it allows greater thoroughness in lipidomics studies and increases scope for answering scientific questions about lipid systems.

scholarly journals Self-Assembly of Hydrogen-Bonded Cage Tetramers of Phosphonic Acid

Symmetry ◽  
2021 ◽  
Vol 13 (2) ◽  
pp. 258 ◽  
Author(s):  
Ivan S. Giba ◽  
Peter M. Tolstoy
Keyword(s):  
Hydrogen Bonds ◽  
Phosphonic Acid ◽  
Self Assembly ◽  
Density Functional ◽  
Proton Donor ◽  
The Self ◽  
Proton Acceptor ◽  
31P Nmr Spectroscopy ◽  
Phosphonic Acids ◽  
Self Association

The self-association of phosphonic acids with general formula RP(O)(OH)2 in solution state remains largely unexplored. The general understanding is that such molecules form multiple intermolecular hydrogen bonds, but the stoichiometry of self-associates and the bonding motifs are unclear. In this work, we report the results of the study of self-association of tert-butylphosphonic acid using low temperature liquid-state 1H and 31P NMR spectroscopy (100 K; CDF3/CDF2Cl) and density functional theory (DFT) calculations. For the first time, we demonstrate conclusively that polar aprotic medium tert-butylphosphonic acid forms highly symmetric cage-like tetramers held by eight OHO hydrogen bonds, which makes the complex quite stable. In these associates. each phosphonic acid molecule is bonded to three other molecules by forming two hydrogen bonds as proton donor and two hydrogen bonds as proton acceptor. Though the structure of such cage-like tetramers is close to tetrahedral, the formal symmetry of the self-associate is C2.

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