Browse
Submit Data
Databases
API
Help

Dataset Information

29 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Synthesis of the Hexasaccharide Fragment of Landomycin A Using a Mild, Reagent-Controlled Approach.

ABSTRACT: The synthesis of the hexasaccharide fragment of landomycin A is reported. Using p-toluenesulfonyl chloride mediated dehydrative glycosylation, we constructed the deoxy-sugar linkages in a stereoselective fashion without the need for temporary prosthetic groups to control selectivity. Through this approach, the hexasaccharide was obtained in 28 steps and 8.9% overall yield, which is an order of magnitude higher than that of previously reported approaches.

SUBMITTER: Yalamanchili S

PROVIDER: S-EPMC6746318 | biostudies-literature | 2019 May

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Synthesis of the Hexasaccharide Fragment of Landomycin A Using a Mild, Reagent-Controlled Approach.

Yalamanchili Subbarao S Lloyd Dina D Bennett Clay S CS

Organic letters 20190425 10

The synthesis of the hexasaccharide fragment of landomycin A is reported. Using p-toluenesulfonyl chloride mediated dehydrative glycosylation, we constructed the deoxy-sugar linkages in a stereoselective fashion without the need for temporary prosthetic groups to control selectivity. Through this approach, the hexasaccharide was obtained in 28 steps and 8.9% overall yield, which is an order of magnitude higher than that of previously reported approaches. ...[more]

PMID: 31021647

Similar Datasets

Synthesis of the Non-Reducing Hexasaccharide Fragment of Saccharomicin B.

Project description:A synthesis of the nonreducing end hexasaccharide of saccharomicin B, α-l-Eva-(1→4)-α-l-Eva-(1→4)-α-l-Dig-(1→4)-α-l-Eva-(1→4)-α-l-Dig-(1→4)-β-d-Fuc, has been developed. Selective glycosylations of l-digitoxose (l-Dig) using AgPF6/TTBP-mediated thioether activation and l-4-e pi-vancosamine (l-Eva) using Tf2O/DTBMP-mediated sulfoxide activation produced the hexasaccharide as a single diastereomer in very good yield. This hexasaccharide is properly functionalized to serve as a glycosyl donor for the total synthesis of saccharomicin B.

| S-EPMC6465119 | biostudies-literature

Reagent-Controlled Synthesis of the Branched Trisaccharide Fragment of the Antibiotic Saccharomicin B.

Project description:A concise synthesis of a branched trisaccharide, ?-l-Dig-(1 ? 3)-[?-l-Eva-(1 ? 4)]-?-d-Fuc, corresponding to saccharomicin B, has been developed via reagent-controlled ?-selective glycosylations. Starting from the d-fucose acceptor, l- epi-vancosamine was selectively installed using 2,3-bis(2,3,4-trimethoxyphenyl)cyclopropene-1-thione/oxalyl bromide mediated dehydrative glycosylation. Following deprotection, l-digitoxose was installed using the AgPF6/TTBP thioether-activation method to produce the trisaccharide as a single ?-anomer. This highly functionalized trisaccharide can potentially serve as both a donor and an acceptor for the total synthesis of the antibiotic saccharomicin B.

| S-EPMC6094932 | biostudies-literature

A chemical synthesis of a multiply 13 C-labeled hexasaccharide: a high-mannose N-glycan fragment.

Project description:As covalent modifiers of proteins, high-mannose N-glycans are important in maintaining protein structure and function in vivo. The conformations of these glycans can be studied by nuclear magnetic resonance spectroscopy using spin-spin couplings (J-couplings; scalar couplings) and other nuclear magnetic resonance parameters that are sensitive to the geometries of their constituent glycosidic linkages and other mobile elements in their structures. These analyses often require 13 C-labeling at specific carbon atoms, especially when measurements of 13 C-13 C J-couplings are of interest. The selection of particular 13 C isotopomers of a glycan depends on the type of question under scrutiny. A chemical synthesis of a mannose-containing hexasaccharide, ?[1-13 C]Man(1?2)?[1,2-13 C2 ]Man(1?6)[?[1-13 C]Man(1?2)?[1,2-13 C2 ]Man(1?3)]?[1,2-13 C2 ]Man(1?6)?ManOCH3 , which is a nested fragment of the high-mannose N-glycans of human glycoproteins and contains eight 13 C-enriched carbon sites, is described in this report. The selected 13 C isotopomer was chosen to maximize the measurement of J-couplings sensitive to linkage conformations. This work demonstrates that chemical syntheses of multiply 13 C-labeled oligosaccharides are technically feasible and practical using present synthetic methods. The availability of this and other multiply 13 C-labeled mannose-containing oligosaccharides will promote future studies of their conformations in solution and in the bound state.

| S-EPMC5177528 | biostudies-literature

Reagent Controlled Stereoselective Synthesis of α-Glucans.

Project description:The development of a general glycosylation method that allows for the stereoselective construction of glycosidic linkages is a tremendous challenge. Because of the differences in steric and electronic properties of the building blocks used, the outcome of a glycosylation reaction can vary greatly when switching form one glycosyl donor-acceptor pair to another. We here report a strategy to install cis-glucosidic linkages in a fully stereoselective fashion that is under direct control of the reagents used to activate a single type of donor building block. The activating reagents are tuned to the intrinsic reactivity of the acceptor alcohol to match the reactivity of the glycosylating agent with the reactivity of the incoming nucleophile. A protecting group strategy is introduced that is based on the sole use of benzyl-ether type protecting groups to circumvent changes in reactivity as a result of the protecting groups. For the stereoselective construction of the α-glucosyl linkages to a secondary alcohol, a per-benzylated glusosyl imidate donor is activated with a combination of trimethylsilyltriflate and DMF, while activation of the same imidate donor with trimethylsilyl iodide in the presence of triphenylphosphine oxide allows for the stereoselective cis-glucosylation of primary alcohols. The effectiveness of the strategy is illustrated in the modular synthesis of a Mycobacterium tuberculosis nonasaccharide, composed of an α-(1-4)-oligoglucose backbone bearing different α-glucosyl branches.

| S-EPMC5890317 | biostudies-literature

Facile chemoenzymatic synthesis of biotinylated heparosan hexasaccharide.

Project description:A biotinylated heparosan hexasaccharide was synthesized using a one-pot multi-enzyme strategy, in situ activation and transfer of N-trifluoroacetylglucosamine (GlcNTFA) to a heparin backbone significantly improved the synthetic efficiency. The biotinylated hexasaccharide could serve as a flexible core to diversify its conversion into heparan sulfate isoforms with potential biological applications and therapeutics.

| S-EPMC4472006 | biostudies-literature

Modular Sulfondiimine Synthesis Using a Stable Sulfinylamine Reagent.

Project description:Sulfondiimines-the double aza-analogues of sulfones-hold significant potential as leads in discovery chemistry, yet their application in this arena has been held back by the scarcity of appropriate synthetic routes. Existing methods employ sulfides as substrates, and rely on consecutive imination reactions using the hazardous reagent O-mesitylenesulfonyl hydroxylamine. Here we report a method for sulfondiimine synthesis that does not begin with a sulfide or a thiol, and instead employs two Grignard reagents and a bespoke sulfinylamine (R-N?S?O) reagent as starting materials. Lewis acid-mediated assembly of these three components provides efficient access to a series of sulfilimine intermediates. A novel rhodium-catalyzed imination of these electron-rich sulfilimines then delivers a varied range of sulfondiimines featuring orthogonal N-functionalization. Conditions for the selective manipulation of both N-atoms of the sulfondiimines are reported, allowing access to a broad range of mono- and difunctionalized products. The oxidation of the sulfilimine intermediates is also described, and provides a complementary route to sulfoximines.

| S-EPMC7007239 | biostudies-literature

Synthesis of a Fluorous-Tagged Hexasaccharide and Interaction with Growth Factors Using Sugar-Coated Microplates.

Project description:Here, we report the synthesis of a sulfated, fully protected hexasaccharide as a glycosaminoglycan mimetic and the study of its interactions with different growth factors: midkine, basic fibroblast growth factor (FGF-2) and nerve growth factor (NGF). Following a fluorous-assisted approach, monosaccharide building blocks were successfully assembled and the target oligosaccharide was prepared in excellent yield. The use of more acid stable 4,6-O-silylidene protected glucosamine units was crucial for the efficiency of this strategy because harsh reaction conditions were needed in the glycosylations to avoid the formation of orthoester side products. Fluorescence polarization experiments demonstrated the strong interactions between the synthesized hexamer, and midkine and FGF-2. In addition, we have developed an alternative assay to analyse these molecular recognition events. The prepared oligosaccharide was non-covalently attached to a fluorous-functionalized microplate and the direct binding of the protein to the sugar-immobilized surface was measured, affording the corresponding KD,surf value.

| S-EPMC6515340 | biostudies-literature

Molecular detection of SARS-CoV-2 using a reagent-free approach.

Project description:Shortage of reagents and consumables required for the extraction and molecular detection of SARS-CoV-2 RNA in respiratory samples has led many laboratories to investigate alternative approaches for sample preparation. Many groups recently presented results using heat processing method of respiratory samples prior to RT-qPCR as an economical method enabling an extremely fast streamlining of the processes at virtually no cost. Here, we present our results using this method and highlight some major pitfalls that diagnostics laboratories should be aware of before proceeding with this methodology. We first investigated various treatments using different temperatures, incubation times and sample volumes to optimise the heat treatment conditions. Although the initial data confirmed results published elsewhere, further investigations revealed unexpected inhibitory properties of some commonly used universal transport media (UTMs) on some commercially available RT-qPCR mixes, leading to a risk of reporting false-negative results. This emphasises the critical importance of a thorough validation process to determine the most suitable reagents to use depending on the sample types to be tested. In conclusion, a heat processing method is effective with very consistent Ct values and a sensitivity of 96.2% when compared to a conventional RNA extraction method. It is also critical to include an internal control to check each sample for potential inhibition.

| S-EPMC7721139 | biostudies-literature

A Formal Synthesis of (+)-Hannokinol Using a Chiral Horner-Wittig Reagent.

Project description:Herein, we report a concise and efficient formal synthesis of (+)-hannokinol. Key to this new strategy is the use of a chiral Horner-Wittig reagent, readily available from 2-deoxy-D-ribose, to introduce the chiral 1,3-diol motif.

| S-EPMC11313872 | biostudies-literature

Mild silver-mediated geminal difluorination of styrenes using an air- and moisture-stable fluoroiodane reagent.

Project description:An air- and moisture-stable fluoroiodane in the presence of AgBF4 is suitable for selective geminal difluorination of styrenes under mild reaction conditions. One of the C?F bonds is formed by transfer of electrophilic fluorine from the hypervalent iodine reagent, while the other one arises from the tetrafluoroborate counterion of silver. Deuterium-isotope-labelling experiments and rearrangement of methyl styrene substrates suggest that the reaction proceeds through a phenonium ion intermediate.

| S-EPMC4501311 | 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