Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Reagent Controlled Direct Dehydrative Glycosylation with 2-Deoxy Sugars: Construction of the Saquayamycin Z Pentasaccharide.

ABSTRACT: The first synthesis of the pentasaccharide fragment of the angucycline antibiotic saquayamycin Z is described. By using our sulfonyl chloride mediated reagent controlled dehydrative glycosylation, we are able to assemble the glycosidic linkages with high levels of anomeric selectivity. The total synthesis was completed in 25 total steps, and in 2.5% overall yield with a longest linear sequence of 15 steps.

SUBMITTER: Mizia JC

PROVIDER: S-EPMC6746326 | biostudies-literature | 2019 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Reagent Controlled Direct Dehydrative Glycosylation with 2-Deoxy Sugars: Construction of the Saquayamycin Z Pentasaccharide.

Mizia J Colin JC Bennett Clay S CS

Organic letters 20190715 15

The first synthesis of the pentasaccharide fragment of the angucycline antibiotic saquayamycin Z is described. By using our sulfonyl chloride mediated reagent controlled dehydrative glycosylation, we are able to assemble the glycosidic linkages with high levels of anomeric selectivity. The total synthesis was completed in 25 total steps, and in 2.5% overall yield with a longest linear sequence of 15 steps. ...[more]

PMID: 31305082

Similar Datasets

Reagent-Controlled α-Selective Dehydrative Glycosylation of 2,6-Dideoxy Sugars: Construction of the Arugomycin Tetrasaccharide.

Project description:The first synthesis of the tetrasaccharide fragment of the anthracycline natural product Arugomycin is described. A reagent controlled dehydrative glycosylation method involving cyclopropenium activation was utilized to synthesize the α-linkages with complete anomeric selectivity. The synthesis was completed in 20 total steps, and in 2.5% overall yield with a longest linear sequence of 15 steps.

| S-EPMC7239334 | biostudies-literature

Direct Dehydrative Glycosylation Catalyzed by Diphenylammonium Triflate.

Project description:Methods for direct dehydrative glycosylations of carbohydrate hemiacetals catalyzed by diphenylammonium triflate under microwave irradiation are described. Both armed and disarmed glycosyl-C1-hemiacetal donors were efficiently glycosylated in moderate to excellent yields without the need for any drying agents and stoichiometric additives. This method has been successfully applied to a solid-phase glycosylation.

| S-EPMC7179217 | biostudies-literature

An Improved Approach to the Direct Construction of 2-Deoxy-?-Linked Sugars: Applications to Oligosaccharide Synthesis.

Project description:A next-generation reagent-controlled approach for the synthesis of 2,6-dideoxy and 2,3,6-trideoxy sugar donors in good yield and high ?-selectivity is reported. The use of p-toluenesulfonyl chloride and potassium hexamethyldisilazide (KHMDS) greatly simplifies deoxy-sugar glycoside construction, and can be used for gram-scale glycosylation reactions. The development of this approach and its application to the construction of ?-linked deoxy-sugar oligosaccharides are described.

| S-EPMC6094935 | biostudies-literature

Polysulfurating reagent design for unsymmetrical polysulfide construction.

Project description:From life science to material science, to pharmaceutical industry, and to food chemistry, polysulfides are vital structural scaffolds. However, there are limited synthetic methods for unsymmetrical polysulfides. Conventional strategies entail two pre-sulfurated cross-coupling substrates, R-S, with higher chances of side reactions due to the characteristic of sulfur. Herein, a library of broad-spectrum polysulfurating reagents, R-S-S-OMe, are designed and scalably synthesized, to which the R-S-S source can be directly introduced for late-stage modifications of biomolecules, natural products, and pharmaceuticals. Based on the hard and soft acids and bases principle, selective activation of sulfur-oxygen bond has been accomplished via utilizing proton and boride for efficient unsymmetrical polysulfuration. These polysulfurating reagents are highlighted with their outstanding multifunctional gram-scale transformations with various nucleophiles under mild conditions. A diversity of polysulfurated biomolecules, such as SS-(+)-δ-tocopherol, SS-sulfanilamide, SS-saccharides, SS-amino acids, and SSS-oligopeptides have been established for drug discovery and development.

| S-EPMC5989225 | biostudies-literature

Site-selective, stereocontrolled glycosylation of minimally protected sugars.

Project description:The identification of general and efficient methods for the construction of oligosaccharides stands as one of the great challenges for the field of synthetic chemistry1,2. Selective glycosylation of unprotected sugars and other polyhydroxylated nucleophiles is a particularly significant goal, requiring not only control over the stereochemistry of the forming bond but also differentiation between similarly reactive nucleophilic sites in stereochemically complex contexts3,4. Chemists have generally relied on multi-step protecting-group strategies to achieve site control in glycosylations, but practical inefficiencies arise directly from the application of such approaches5-7. Here we describe a strategy for small-molecule-catalyst-controlled, highly stereo- and site-selective glycosylations of unprotected or minimally protected mono- and disaccharides using precisely designed bis-thiourea small-molecule catalysts. Stereo- and site-selective galactosylations and mannosylations of a wide assortment of polyfunctional nucleophiles is thereby achieved. Kinetic and computational studies provide evidence that site-selectivity arises from stabilizing C-H/π interactions between the catalyst and the nucleophile, analogous to those documented in sugar-binding proteins. This work demonstrates that highly selective glycosylation reactions can be achieved through control of stabilizing non-covalent interactions, a potentially general strategy for selective functionalization of carbohydrates.

| S-EPMC9427130 | biostudies-literature

Stereoselective Construction of β-chiral Homoallyl Functionalities by Substrate- and Reagent-Controlled Iterative 1,2-Metallate Rearrangements.

Project description:Homoallylic alcohols possessing chiral β-centers are considered highly valuable in the synthesis of polyketide-based natural products. Therefore, there is a significant demand for new methods that allow for their stereoselective access. In pursuit of this objective, we have successfully combined our substrate-controlled protocol of Hoppe-Matteson-Aggarwal chemistry with iterative 1,2-metallate rearrangements. Notably, this approach has proven effective in introducing not only primary alcohols but also other functional groups such as alkynes and protected amines.

| S-EPMC10683368 | biostudies-literature

A new reagent for direct difluoromethylation.

Project description:Molecular scaffolds containing alkylfluorine substituents are desired in many areas of chemical research from materials to pharmaceuticals. Herein, we report the invention of a new reagent (Zn(SO(2)CF(2)H)(2), DFMS) for the innate difluoromethylation of organic substrates via a radical process. This mild, operationally simple, chemoselective, and scalable difluoromethylation method is compatible with a range of nitrogen-containing heteroarene substrates of varying complexity as well as select classes of conjugated ?-systems and thiols. Regiochemical comparisons suggest that the CF(2)H radical generated from the new reagent possesses nucleophilic character.

| S-EPMC3269891 | biostudies-literature

Chemical Synthesis and Immunological Evaluation of a Pentasaccharide Bearing Multiple Rare Sugars as a Potential Anti-pertussis Vaccine.

Project description:With the infection rate of Bordetella pertussis at a 60-year high, there is an urgent need for new anti-pertussis vaccines. The lipopolysaccharide (LPS) of B. pertussis is an attractive antigen for vaccine development. With the presence of multiple rare sugars and unusual glycosyl linkages, the B. pertussis LPS is a highly challenging synthetic target. In this work, aided by molecular dynamics simulation and modeling, a pertussis-LPS-like pentasaccharide was chemically synthesized for the first time. The pentasaccharide was conjugated with a powerful carrier, bacteriophage Qβ, as a vaccine candidate. Immunization of mice with the conjugate induced robust anti-glycan IgG responses with IgG titers reaching several million enzyme-linked immunosorbent assay (ELISA) units. The antibodies generated were long lasting and boostable and could recognize multiple clinical strains of B. pertussis, highlighting the potential of Qβ-glycan as a new anti-pertussis vaccine.

| S-EPMC7141973 | biostudies-literature

Silver Nanoparticle Formation-Based Colorimetric Determination of Reducing Sugars in Food Extracts via Tollens' Reagent.

Project description:A simple, sensitive, and nonenzymatic nanospectrophotometric method was developed for the determination of reducing sugars. The silver mirror reaction-assisted method is based on the in situ formation of silver nanoparticles in the presence of reducing sugars. All simple reducing sugars (glucose, galactose, fructose, mannose, maltose, and lactose) examined had perfectly linear regression equations. The detection limit for glucose was 40 nM. The proposed method could be selectively applied to various synthetic mixtures of reducing sugars with polyphenolic compounds, and to honey, milk, and commercial fruit juice as real samples using solid phase extraction as a clean-up process. The developed method was also statistically validated against conventional alkaline CUPRAC (cupric-neocuproine, Cu(II)-Nc) spectrophotometric method using Student's t- and F-tests.

| S-EPMC6647951 | biostudies-literature

Enhancing Terpene yield from sugars via novel routes to 1-deoxy-d-xylulose 5-phosphate.

Project description:Terpene synthesis in the majority of bacterial species, together with plant plastids, takes place via the 1-deoxy-d-xylulose 5-phosphate (DXP) pathway. The first step of this pathway involves the condensation of pyruvate and glyceraldehyde 3-phosphate by DXP synthase (Dxs), with one-sixth of the carbon lost as CO2. A hypothetical novel route from a pentose phosphate to DXP (nDXP) could enable a more direct pathway from C5 sugars to terpenes and also circumvent regulatory mechanisms that control Dxs, but there is no enzyme known that can convert a sugar into its 1-deoxy equivalent. Employing a selection for complementation of a dxs deletion in Escherichia coli grown on xylose as the sole carbon source, we uncovered two candidate nDXP genes. Complementation was achieved either via overexpression of the wild-type E. coli yajO gene, annotated as a putative xylose reductase, or via various mutations in the native ribB gene. In vitro analysis performed with purified YajO and mutant RibB proteins revealed that DXP was synthesized in both cases from ribulose 5-phosphate (Ru5P). We demonstrate the utility of these genes for microbial terpene biosynthesis by engineering the DXP pathway in E. coli for production of the sesquiterpene bisabolene, a candidate biodiesel. To further improve flux into the pathway from Ru5P, nDXP enzymes were expressed as fusions to DXP reductase (Dxr), the second enzyme in the DXP pathway. Expression of a Dxr-RibB(G108S) fusion improved bisabolene titers more than 4-fold and alleviated accumulation of intracellular DXP.

| S-EPMC4272731 | 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