A novel approach to phosphonic acids from hypophosphorous acid.
Ontology highlight
ABSTRACT:
SUBMITTER: Bravo-Altamirano K
PROVIDER: S-EPMC2031837 | biostudies-literature | 2007 Aug
REPOSITORIES: biostudies-literature
Publications
A novel approach to phosphonic acids from hypophosphorous acid.
Bravo-Altamirano Karla K Montchamp Jean-Luc JL
Tetrahedron letters 20070801 33
A novel access to phosphonic acids via Pd-catalyzed tandem carbon-phosphorus bond formation - oxidation processes was developed. The procedures involve atom-economical and environmentally friendly functionalization reactions of hypophosphorous acid (H(3)PO(2)) and H-phosphinic acids [RP(O)(OH)(H)]. ...[more]
Similar Datasets
Project description: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.
| S-EPMC8466293 | biostudies-literature
Project description:Natural products containing carbon-phosphorus bonds (phosphonic and phosphinic acids) have found widespread use in medicine and agriculture. Recent years have seen a renewed interest in the biochemistry and biology of these compounds with the cloning of the biosynthetic gene clusters for several family members. This review discusses the commonalities and differences in the molecular logic that lie behind the biosynthesis of these compounds. The current knowledge regarding the metabolic pathways and enzymes involved in the production of a number of natural products, including the approved antibiotic fosfomycin, the widely used herbicide phosphinothricin (PT), and the clinical candidate for treatment of malaria FR-900098, is presented. Many of the enzymes involved in the biosynthesis of these compounds catalyze chemically and biologically unprecedented transformations, and a wealth of new biochemistry has been revealed through their study. These investigations have also suggested new strategies for natural product discovery.
| S-EPMC2729427 | biostudies-literature
Project description:The combined benefits of moisture-stable phosphonic acids and mesoporous silica materials (SBA-15 and MCM-41) as large-surface-area solid supports offer new opportunities for several applications, such as catalysis or drug delivery. We present a comprehensive study of a straightforward synthesis method via direct immobilization of several phosphonic acids and phosphoric acid esters on various mesoporous silicas in a Dean⁻Stark apparatus with toluene as the solvent. Due to the utilization of azeotropic distillation, there was no need to dry phosphonic acids, phosphoric acid esters, solvents, or silicas prior to synthesis. In addition to modeling phosphonic acids, immobilization of the important biomolecule adenosine monophosphate (AMP) on the porous supports was also investigated. Due to the high surface area of the mesoporous silicas, a possible catalytic application based on immobilization of an organocatalyst for an asymmetric aldol reaction is discussed.
| S-EPMC6409583 | biostudies-literature
Project description:Two different phosphonic acid monolayer films for immobilization of bioactive molecules such as the protein BMP-2 on titanium surfaces have been prepared. Monolayers of (11-hydroxyundecyl)phosphonic acid and (12-carboxydodecyl)phosphonic acid molecules were produced by a simple dipping process (the T-BAG method). The terminal functional groups on these monolayers were activated (carbonyldiimidazole for hydroxyl groups and N-hydroxysuccinimide for carboxyl groups) to bind amine-containing molecules. The reactivity of the surfaces was investigated using trifluoroethylamine hydrochloride and BMP-2. Each step of the surface modification procedure was characterized by X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry.
| S-EPMC2597787 | biostudies-literature
Project description:Osteoporosis is a skeletal disease associated with excessive bone turnover. Among the compounds with antiresorptive activity, nitrogen-containing bisphosphonates play the most important role in antiosteoporotic treatment. In previous studies, we obtained two aminomethylidenebisphosphonates-benzene-1,4-bis[aminomethylidene(bisphosphonic)] (WG12399C) acid and naphthalene-1,5-bis[aminomethylidene(bisphosphonic)] (WG12592A) acid-which showed a significant antiproliferative activity toward J774E macrophages, a model of osteoclast precursors. The aim of these studies was to evaluate the antiresorptive activity of these aminobisphosphonates in ovariectomized (OVX) Balb/c mice. The influence of WG12399C and WG12592A administration on bone microstructure and bone strength was studied. Intravenous injections of WG12399C and WG12592A bisphosphonates remarkably prevented OVX-induced bone loss; for example, they sustained bone mineral density at control levels and restored other bone parameters such as trabecular separation. This was accompanied by a remarkable reduction in the number of TRAP-positive cells in bone tissue. However, a significant improvement in the quality of bone structure did not correlate with a parallel increase in bone strength. In ex vivo studies, WG12399C and WG12592A remarkably bisphosphonates reduced osteoclastogenesis and partially inhibited the resorptive activity of mature osteoclasts. Our results show interesting biological activity of two aminobisphosphonates, which may be of interest in the context of antiresorptive therapy.
| S-EPMC8430618 | biostudies-literature
Project description:Lower rim O-methyl, -n-butyl, and n-octadecyl calix[4]arenes bearing p-phosphonic acid groups on the upper rim have been prepared in high yield, compounds 12-14. Where possible the compounds have been characterized in the solid state using X-ray diffraction, or as the precursor phosphate esters or a cesium salt. The cone conformation ethyl phosphate ester for the octadecyl compound crystallizes in a bi-layer 39.1 A thick which approaches the 40 A of biological membranes. The 1,3-alternate cone conformation of the cesium salt of the O-methyl phosphonic acid has a metal ion coordinated to two methoxy groups, four O-P (two from neighboring calixarenes), and two eta(3)-C(3) moieties from two 1,3-disposed aromatic rings. MALDI-TOF spectra of compounds 12-14 show successive peaks corresponding to 15, 33 and 16 calixarene units, which is consistent with the intra-molecular H-bonding capabilities of the di-protic phosphonic acid groups where the calixarenes are arranged into layers, including bilayers.
| S-EPMC2723774 | biostudies-literature
Project description:Hexamethoxy-calix[6]arene has been fully functionalized with p-phosphonic acid groups on the upper rim in 57% yield over three steps, and has been authenticated in the solid state by X-ray diffraction as either a nitrate salt or one of two calcium complexes. The latter differ by the ratio of calcium ions per calixarene, either 3:1 or 4:1. In both structures the coordination sphere of the calcium ions is made up of oxygen atoms from the phosphonic acid groups and from water of crystallization, as part of extended polymeric layers in the extended 3D packing. Hirshfeld surface analysis shows extensive O...H and O...Ca interactions for the phosphonic acid moieties in both calcium structures. MALDI-TOF MS of the hexaphosphonic acid shows nano-arrays consisting of up to a maximum of 28 calixarene units.
| S-EPMC2906806 | biostudies-literature
Project description:Novel triethoxysilane and dimethyl phosphonate functional vinylidene fluoride (VDF)-containing terpolymers, for potential applications in Eu ion extraction from water, were produced by conventional radical terpolymerization of VDF with vinyltriethoxylsilane (VTEOS) and vinyldimethylphosphonate (VDMP). Although initial attempts for the copolymerization of VTEOS and VDMP failed, the successful terpolymerization was initiated by peroxide to lead to multiple poly(VDF-ter-VDMP-ter-VTEOS) terpolymers, that had different molar percentages of VDF (70-90 mol.%), VTEOS (5-20 mol.%) and VDMP (10 mol.%) in 50-80% yields. The obtained terpolymers were characterized by 1H, 19F, 29Si and 31P NMR spectroscopies. The crosslinking of such resulting poly(VDF-ter-VDMP-ter-VTEOS) terpolymers was achieved by hydrolysis and condensation (sol-gel process) of the triethoxysilane groups in acidic media, to obtain a 3D network, which was analyzed by solid state 29Si and 31P NMR spectroscopies, TGA and DSC. The thermal stability of the terpolymers was moderately high (up to 300 °C under air), whereas they display a slight increase in their crystallinity-rate from 9.7% to 12.1% after crosslinking. Finally, the dimethyl phosphonate functions were hydrolyzed into phosphonic acid successfully, and the europium ion extraction capacity of terpolymer was studied. The results demonstrated a very high removal capacity of Eu(III) ions from water, up to a total removal at low concentrations.
| S-EPMC7563938 | biostudies-literature
Project description: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 N(5)-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.
| S-EPMC4593130 | biostudies-literature
Project description:Autotaxin is an extracellular phospholipase D that catalyzes the hydrolysis of lysophosphatidyl choline (LPC) to bioactive lipid lysophosphatidic acid (LPA). LPA has been implicated in many pathological processes relevant to cancer, including cell migration and invasion, proliferation, and survival. The most potent autotaxin inhibitor described to date is the LPA analogue S32826 (IC50 5.6 nM). S32826 and many other autotaxin inhibitors are notably lipophilic, creating a need to improve their physical properties. Polymers are becoming an increasingly useful tool in the delivery of drugs and have the potential to improve the properties of small molecules. Herein we report the synthesis of a S32826 dendrimer conjugate and its biological evaluation. The conjugate was found to inhibit autotaxin activity using two different substrates and to decrease the migration of an ovarian cancer cell line modified to overexpress autotaxin. Furthermore, the conjugate potentiated activation of caspase 3/7 induced by carboplatin.
| S-EPMC4027627 | biostudies-literature