Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Phosphine Mediated Conjugation of S-Nitrosothiols and Aldehydes.

ABSTRACT: S-Nitrosothiols (SNO) and their biological implications as an important post-translational modification are under active investigation. In our work on bioorthogonal reactions of protein SNO we have uncovered chemistry of this functionality that shows synthetic promise. Herein we report a phosphine-mediated reaction between SNO and aldehydes to form thioimines. A simple synthesis of benzoisothiazole based on this reaction is presented.

SUBMITTER: Biggs TD

PROVIDER: S-EPMC4467916 | biostudies-literature | 2015 May

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Phosphine Mediated Conjugation of S-Nitrosothiols and Aldehydes.

Biggs Tyler D TD Weerasinghe Laksiri L Park Chung-Min CM Xian Ming M

Tetrahedron letters 20150501 21

S-Nitrosothiols (SNO) and their biological implications as an important post-translational modification are under active investigation. In our work on bioorthogonal reactions of protein SNO we have uncovered chemistry of this functionality that shows synthetic promise. Herein we report a phosphine-mediated reaction between SNO and aldehydes to form thioimines. A simple synthesis of benzoisothiazole based on this reaction is presented. ...[more]

PMID: 26089576

Similar Datasets

Alcohol-assisted phosphine catalysis: one-step syntheses of dihydropyrones from aldehydes and allenoates.

Project description:This paper describes the phosphine-catalyzed annulation of methyl allenoate with various aromatic aldehydes to form 6-aryl-4-methoxy-5,6-dihydro-2-pyrones. In this reaction, the addition of an alcohol was necessary to induce dihydropyrone formation, with the optimal agent being methanol. Moreover, the addition of n-butyllithium suppressed the formation of the noncyclized product, leading to the exclusive isolation of the dihydropyrone. This method provides an efficient, one-step route toward disubstituted dihydropyrones from simple, stable starting materials.

| S-EPMC2532593 | biostudies-literature

Reductive ligation mediated one-step disulfide formation of S-nitrosothiols.

Project description:A one-step reductive ligation mediated disulfide formation of S-nitrosothiols was developed. This reaction involves the reaction of the S-nitroso group with phosphine-thioesters to form sulfenamide and thiolate intermediates, which then undergo a fast intermolecular disulfide formation to form stable conjugates. This reaction can be used to design new biosensors of S-nitrosated proteins.

| S-EPMC2943486 | biostudies-literature

Ascorbate attenuates red light mediated vasodilation: Potential role of S-nitrosothiols.

Project description:There is significant therapeutic advantage of nitric oxide synthase (NOS) independent nitric oxide (NO) production in maladies where endothelium, and thereby NOS, is dysfunctional. Electromagnetic radiation in the red and near infrared region has been shown to stimulate NOS-independent but NO-dependent vasodilation, and thereby has significant therapeutic potential. We have recently shown that red light induces acute vasodilatation in the pre-constricted murine facial artery via the release of an endothelium derived substance. In this study we have investigated the mechanism of vasodilatation and conclude that 670?nm light stimulates vasodilator release from an endothelial store, and that this vasodilator has the characteristics of an S-nitrosothiol (RSNO). This study shows that 670?nm irradiation can be used as a targeted and non-invasive means to release biologically relevant amounts of vasodilator from endothelial stores. This raises the possibility that these stores can be pharmacologically built-up in pathological situations to improve the efficacy of red light treatment. This strategy may overcome eNOS dysfunction in peripheral vascular pathologies for the improvement of vascular health.

| S-EPMC6156744 | biostudies-literature

Π-Clamp-mediated cysteine conjugation.

Project description:Site-selective functionalization of complex molecules is one of the most significant challenges in chemistry. Typically, protecting groups or catalysts must be used to enable the selective modification of one site among many that are similarly reactive, and general strategies that selectively tune the local chemical environment around a target site are rare. Here, we show a four-amino-acid sequence (Phe-Cys-Pro-Phe), which we call the 'π-clamp', that tunes the reactivity of its cysteine thiol for site-selective conjugation with perfluoroaromatic reagents. We use the π-clamp to selectively modify one cysteine site in proteins containing multiple endogenous cysteine residues. These examples include antibodies and cysteine-based enzymes that would be difficult to modify selectively using standard cysteine-based methods. Antibodies modified using the π-clamp retained binding affinity to their targets, enabling the synthesis of site-specific antibody-drug conjugates for selective killing of HER2-positive breast cancer cells. The π-clamp is an unexpected approach to mediate site-selective chemistry and provides new avenues to modify biomolecules for research and therapeutics.

| S-EPMC4861612 | biostudies-literature

Phosphine-Mediated Iterative Arene Homologation Using Allenes.

Project description:A PPh3-mediated multicomponent reaction between o-phthalaldehydes, nucleophiles, and monosubstituted allenes furnishes functionalized non-C2-symmetric naphthalenes in synthetically useful yields. When the o-phthalaldehydes were reacted with 1,3-disubstituted allenes in the presence of PPh2Et, naphthalene derivatives were also obtained in up to quantitative yields. The mechanism of the latter transformation is straightforward: aldol addition followed by Wittig olefination and dehydration. The mechanism of the former is a tandem ?-umpolung/aldol/Wittig/dehydration process, as established by preparation of putative reaction intermediates and mass spectrometric analysis. This transformation can be applied iteratively to prepare anthracenes and tetracenes using carboxylic acids as pronucleophiles.

| S-EPMC4915745 | biostudies-literature

A phosphine-mediated conversion of azides into diazo compounds.

Project description:N2 the mild: Diazo compounds are extremely versatile intermediates for synthetic organic chemistry, but their synthesis can be challenging in the presence of delicate functional groups. The Staudinger ligation has inspired a mild method for the conversion of a broad range of azides into their diazo compound derivatives through an acyl triazene intermediate.

| S-EPMC3128508 | biostudies-literature

Gold(I) phosphine mediated selective inhibition of lymphoid tyrosine phosphatase.

Project description:Selective protein tyrosine phosphatase (PTP) inhibition is often difficult to achieve owing to the high degree of similarity of the catalytic domains of this family of enzymes. Selective inhibitors of the lymphoid specific tyrosine phosphatase, LYP, are of great interest due to the involvement of LYP in several autoimmune disorders. This manuscript describes a study into the mechanistic details of selective LYP inhibition by a Au(I)-phosphine complex. The complex, [Au((CH(2)CH(2)CN)(2)PPh)Cl], selectively inhibits LYP activity both in vitro and in cells, but does not inhibit other T-cell derived PTPs including the highly homologous PTP-PEST. The mode of inhibition was probed by investigating inhibition of LYP, the LYP mutant C129/231S, and PTP-PEST. Inhibition of LYP and PTP-PEST was competitive, while the LYP double mutant appeared mixed. Wild-type LYP was inhibited more potently than LYP C129/231S, indicating an important role for at least one of these residues in Au(I) binding. Coordination of Au(I) by both the active site cysteine residue as well as either Cys129 or 231 is suggested as a potential mechanism for LYP selective inhibition.

| S-EPMC2873867 | biostudies-literature

Convergent Synthesis of Polysubstituted Furans via Catalytic Phosphine Mediated Multicomponent Reactions.

Project description:Tri- or tetrasubstituted furans have been prepared from terminal activated olefins and acyl chlorides or anhydrides by a multicomponental convergent synthesis mode. Instead of stoichiometric nBu3P, only catalytic nBu3P or nBu3P=O is needed to furnish the furans in modest to excellent yields with a good functional group tolerance under the aid of reducing agent silane. This synthetic method features a silane-driven catalytic intramolecular Wittig reaction as a key annulation step and represents the first successful application of catalytic Wittig reaction in multicomponent cascade reaction.

| S-EPMC6943692 | biostudies-literature

Synthesis of aryl-thioglycopeptides through chemoselective Pd-mediated conjugation.

Project description:We describe herein a Pd-catalyzed methodology for the thioglycoconjugation of iodoaryl peptides and aminoacids. This operationally simple process occurs under semi-aqueous conditions and displays wide substrate scope. The strategy has been successfully applied to both the thioglycosylation of unprotected peptides and the generation of thioglyco-aminoacid building blocks, including those suitable for solid phase peptide synthesis. To demonstrate the broad potential of this technique for late stage functionalization, we successfully incorporated challenging unprotected β-S-GlcNAc- and α-S-GalNAc-derivatives into very long unprotected peptides. This study opens the way to new applications in chemical biology, considering the well-recognized advantages of S-glycosides over O-glycosides in terms of resistance towards both enzymatic and chemical degradation.

| S-EPMC6295873 | biostudies-literature

Bi-mediated allylation of aldehydes in [bmim][Br]: a mechanistic investigation.

Project description:The inexpensive room temperature ionic liquid (RTIL), [bmim][Br] has been found to be a superior medium for the Bi-mediated Barbier-type allylation of aldehydes compared to other conventional solvents. It plays the dual role of a solvent and a metal activator enabling higher yields of the products in a shorter reaction time using stoichiometric/near-stoichiometric amounts of reagents. Plausibly, [bmim][Br] activates Bi metal by a charge transfer mechanism. The 1H VT-NMR studies suggested that both the allylating species, allylbismuth dibromide and diallylbismuth bromide, are generated in situ.

| S-EPMC6122318 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

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