Browse
Submit Data
Databases
API
Help

Dataset Information

13 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Amide Synthesis through the In Situ Generation of Chloro- and Imido-Phosphonium Salts.

ABSTRACT: We describe a methodology for the amidation of carboxylic acids by generating phosphonium salts in situ from N-chlorophthalimide and triphenylphosphine. Aliphatic, benzylic, and aromatic carboxylic acids can be transformed into their amide counter parts using primary and secondary amines. This functional group interconversion is achieved at room temperature in good to excellent yields. Mechanistic work shows the in situ formation of chloro- and imido-phosphonium salts that react as activating agents for carboxylic acids and generate an acyloxy-phosphonium species.

SUBMITTER: Irving CD

PROVIDER: S-EPMC7331200 | biostudies-literature | 2020 Jun

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Amide Synthesis through the In Situ Generation of Chloro- and Imido-Phosphonium Salts.

Irving Charles D CD Floreancig Jack T JT Laulhé Sébastien S

ACS omega 20200619 25

We describe a methodology for the amidation of carboxylic acids by generating phosphonium salts in situ from <i>N</i>-chlorophthalimide and triphenylphosphine. Aliphatic, benzylic, and aromatic carboxylic acids can be transformed into their amide counter parts using primary and secondary amines. This functional group interconversion is achieved at room temperature in good to excellent yields. Mechanistic work shows the in situ formation of chloro- and imido-phosphonium salts that react as activa ...[more]

PMID: 32637849

Similar Datasets

Ferrocene-Containing Sterically Hindered Phosphonium Salts.

Project description:The synthesis and physical properties of the series of the ferrocenyl-containing sterically hindered phosphonium salts based on di(tert-butyl)ferrocenylphosphine is reported. Analysis of voltamogramms of the obtained compounds revealed some correlations between their structures and electrochemical properties. The elongation of the alkyl chain at the P atom as well as replacement of the Br- anion by [BF?]- shifts the ferrocene/ferrocenium transition of the resulting salts into the positive region. DFT results shows that in the former case, the Br- anion destabilizes the corresponding ion pair, making its oxidation easier due to increased highest occupied molecular orbital (HOMO) energy. Increased HOMO energy for ion pairs with the Br- ion compared to BF?- are caused by contribution of bromide atomic orbitals to the HOMO. The observed correlations can be used for fine-tuning the properties of the salts making them attractive for applications in multicomponent batteries and capacitors.

| S-EPMC6278326 | biostudies-literature

Ion-Pair-Directed Borylation of Aromatic Phosphonium Salts.

Project description:Control of positional selectivity in C-H activation reactions remains a challenge for synthetic chemists. Noncovalent catalysis has the potential to be a powerful strategy to address this challenge. As a part of our ongoing investigations into the use of ion-pairing interactions in site-selective catalysis, we demonstrate that several classes of aromatic phosphonium salts undergo iridium-catalyzed C-H borylation with a high selectivity for the arene meta position. This is achieved using a bifunctional bipyridine ligand bearing a pendant sulfonate group, which had previously been successful for borylation of aromatic ammonium salts. In this case, the phosphonium salts give a higher meta selectivity than the corresponding ammonium salts. We propose that the high selectivity occurs due to an attractive electrostatic interaction between the substrate and the ligand in the transition state for borylation.

| S-EPMC6804313 | biostudies-literature

Sterically Hindered Phosphonium Salts: Structure, Properties and Palladium Nanoparticle Stabilization.

Project description:A new family of sterically hindered alkyl(tri-tert-butyl) phosphonium salts (n-CnH2n+1 with n = 2, 4, 6, 8, 10, 12, 14, 16, 18, 20) was synthesized and evaluated as stabilizers for the formation of palladium nanoparticles (PdNPs), and the prepared PdNPs, stabilized by a series of phosphonium salts, were applied as catalysts of the Suzuki cross-coupling reaction. All investigated phosphonium salts were found to be excellent stabilizers of metal nanoparticles of small catalytically active size with a narrow size distribution. In addition, palladium nanoparticles exhibited exceptional stability: the presence of phosphonium salts prevented agglomeration and precipitation during the catalytic reaction.

| S-EPMC7763823 | biostudies-literature

Direct catalytic transformation of white phosphorus into arylphosphines and phosphonium salts.

Project description:Phosphorus compounds are ubiquitous in the chemical sciences, finding applications throughout industry and academia. Of particular interest to synthetic chemists are organophosphorus compounds, which contain P-C bonds. However, state-of-the-art processes for the synthesis of these important materials rely on an inefficient, stepwise methodology involving initial oxidation of white phosphorus (P4) with hazardous chlorine gas and the subsequent displacement of chloride ions. Catalytic P4 organofunctionalisation reactions have remained elusive, as they require multiple P-P bond breaking and P-C bond formation events to break down the P4 core, all of which must occur in a controlled manner. Herein, we describe an efficient transition metal-catalyzed process capable of forming P-C bonds from P4. Using blue light photocatalysis, this method directly affords valuable triarylphosphines and tetraarylphosphonium salts in a single reaction step.

| S-EPMC6914361 | biostudies-literature

Synthesis of Tungsten Imido Alkylidene Complexes that Contain an Electron-Withdrawing Imido Ligand.

Project description:Tungsten NArR alkylidene complexes have been prepared that contain the electron-withdrawing ArR groups 2,4,6-X3C6H2 (ArX3, X = Cl, Br), 2,6-Cl2-4-CF3C6H2 (ArCl2CF3), and 3,5-(CF3)2C6H3 (Ar(CF3)2). Reported complexes include W(NArR)2Cl2(dme) (dme = 1,2-dimethoxyethane), W(NArR)2(CH2CMe3)2, W(NArR)(CHCMe3)(OTf)2(dme), and W(NArR)(CHCMe3)(ODBMP)2 (DBMP = 4-Me-2,6-(CHPh2)C6H2). The W(NArR)(CHCMe3)(ODBMP)2 complexes were explored as initiators for the polymerization of 2,3-dicarbomethoxynorbornadiene (DCMNBD).

| S-EPMC4195510 | biostudies-literature

Sterically Hindered Quaternary Phosphonium Salts (QPSs): Antimicrobial Activity and Hemolytic and Cytotoxic Properties.

Project description:Structure-activity relationships are important for the design of biocides and sanitizers. During the spread of resistant strains of pathogenic microbes, insights into the correlation between structure and activity become especially significant. The most commonly used biocides are nitrogen-containing compounds; the phosphorus-containing ones have been studied to a lesser extent. In the present study, a broad range of sterically hindered quaternary phosphonium salts (QPSs) based on tri-tert-butylphosphine was tested for their activity against Gram-positive (Staphylococcus aureus, Bacillus cereus, Enterococcus faecalis) and Gram-negative (Escherichia coli, Pseudomonas aeruginosa) bacteria and fungi (Candida albicans, Trichophyton mentagrophytes var. gypseum). The cation structure was confirmed to determine their biological activity. A number of QPSs not only exhibit high activity against both Gram-positive and -negative bacteria but also possess antifungal properties. Additionally, the hemolytic and cytotoxic properties of QPSs were determined using blood and a normal liver cell line, respectively. The results show that tri-tert-butyl(n-dodecyl)phosphonium and tri-tert-butyl(n-tridecyl)phosphonium bromides exhibit both low cytotoxicity against normal human cells and high antimicrobial activity against bacteria, including methicillin-resistant strains S. aureus (MRSA). The mechanism of QPS action on microbes is discussed. Due to their high selectivity for pathogens, sterically hindered QPSs could serve as effective tunable biocides.

| S-EPMC8744835 | biostudies-literature

Cobalt-Catalyzed Alkylation of Drug-Like Molecules and Pharmaceuticals Using Heterocyclic Phosphonium Salts.

Project description:Alkylated pyridines are common in pharmaceuticals, and metal catalysis is frequently used to prepare this motif via Csp2-Csp3 coupling processes. We present a cobalt-catalyzed coupling reaction between pyridine phosphonium salts and alkylzinc reagents that can be applied to complex drug-like fragments and for late-stage functionalization of pharmaceuticals. The reaction generally proceeds at room temperature, and 4-position pyridine C-H bonds are the precursors in this strategy. Given the challenges in selectively installing (pseudo)halides in complex pyridines, this two-step process enables sets of molecules to be alkylated that would be challenging using traditional cross-coupling methods.

| S-EPMC6814195 | biostudies-literature

A Strategy to Aminate Pyridines, Diazines, and Pharmaceuticals via Heterocyclic Phosphonium Salts.

Project description:A straightforward process to aminate pyridines and diazines is presented by reacting phosphonium salt derivatives with sodium azide. The iminophosphorane products are versatile precursors to several nitrogen-containing functional groups, and the process can be applied to building block heterocycles, to drug-like fragments, and for late-stage functionalization of complex pharmaceuticals. Appealing features of this strategy include using C-H bonds as precursors, precise regioselectivity, and a distinct scope from other amination methods, particularly those relying on halogenated azaarenes.

| S-EPMC6250567 | biostudies-other

4-Chloro-benzothio-amide.

Project description:In the title compound, C(7)H(6)ClNS, the dihedral angle between the aromatic ring and the thio-amide fragment is 28.1?(2)°. The structure features a ?-stacking inter-action between the aromatic rings with a slight offset of the rings, giving a centroid-centroid separation of 3.7942?(2)?Å. There are inter-molecular hydrogen-bonding inter-actions between the amino group and the S atoms.

| S-EPMC2977801 | biostudies-other

SAR Studies of Diphenyl Cationic Trypanocides: Superior Activity of Phosphonium over Ammonium Salts.

Project description:In previous studies, we have shown that phosphonium salt diphenyl derivatives are attractive antitrypanosomal hit compounds with EC50 values against Trypanosoma brucei in the nanomolar range. To evaluate the role of the cationic center on the trypanocidal activity and extend the structure-activity relationship (SAR) of this series, trialkylammonium, pyridinium, and quinolinium salt analogues were synthesized and evaluated in vitro against T. b. brucei. Similar SARs were observed with ammonium and phosphonium salts showing that charge dispersion and lipophilic groups around the cationic center are crucial to obtain submicromolar activities. The new compounds were equally effective against wild type (T. b. brucei s427) and resistant strains (TbAT1-KO and TbB48) of trypanosomes indicating that the P2 and high affinity pentamidine transporters (HAPT) are not essential to their trypanocidal action. Similarly to phosphonium salt derivatives, diffusion seems to be the main route of entry into trypanosomes.

| S-EPMC4329581 | biostudies-other

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data