56586-54-0

Upstream product

• 120408-72-2 Methyl 2,3-anhydro-4,6-O-(phenylmethylene)-β-D-allopyranoside 
• 3162-96-7 4,6-O-benzylidene-1-O-methyl-α-D-glucopyranoside 
• 98-87-3 benzylidene dichloride 
• 10227-29-9 methyl 2,3-di-O-methyl-α-D-glucopyranoside 
• 74-88-4 methyl iodide 
• 56-23-5 tetrachloromethane 
• 77-78-1 dimethyl sulfate 
• 100-52-7 benzaldehyde 
• 3162-96-7 methyl 4,6-O-benzylidene-α-D-glucopyranoside 
• 97-30-3 methyl-alpha-D-glucopyranoside 
• 1152-39-2 p-methylphenyl 1-thio-β-D-glucopyranoside 
• 28244-94-2 4-methylphenyl 2,3,4,6-tetra-O-acetyl-1-thio-β-D-galactopyranoside 
• 3013-58-9 methyl 4,6-O-benzylidene-2,3-di-O-methyl-α,D-glucopyranoside 
• 64552-06-3 methyl 4,6-O-benzylidene-α-D-galactopyranoside 

Downstream Products

• 51517-51-2 methyl 6-O-benzoyl-2,3-di-O-methyl-α-D-glucopyranoside 
• 56543-16-9 methyl 4-O-benzoyl-2,3-di-O-methyl-α-D-glucopyranoside 
• 100-52-7 benzaldehyde 
• 10227-29-9 methyl 2,3-di-O-methyl-α-D-glucopyranoside 
• 83075-53-0 methyl 4-O-benzyl-2,3-di-O-methyl-α-D-glucopyranoside 
• 82159-70-4 methyl 4-O-benzoyl-6-deoxy-2,3-di-O-methyl-α-D-glucopyranoside 
• 178319-42-1 methyl 4-O-benzyl-2,3,6-tri-O-methyl-α-D-glucopyranoside 
• 106220-89-7 methyl 6-O-benzyl-2,3-di-O-methyl-α-D-glucopyranoside 
• 196801-96-4 methyl 4-O-benzyl-2,3-di-O-methyl-6-O-triphenylmethyl-α-D-glucopyranoside 
• 51016-10-5 methyl 2,3-di-O-methyl-6-O-(triphenylmethyl)-α-D-glucopyranoside 
• 1384974-90-6 1,6-anhydro-2,3-di-O-methyl-5-C-methoxy-4-O-benzyl-β-L-idopyranose 
• 1384974-91-7 1,6-anhydro-2,3-di-O-methyl-4-O-benzyl-5-C-trifluoromethanesulfonyloxy-β-L-idopyranose 
• 1384974-93-9 1,6-anhydro-2,3-di-O-methyl-5-C-phenoxycarbonate-4-O-benzyl-β-L-idopyranose 
• 1384974-95-1 (4S,5S,6R,7R)-4-benzyloxy-7-chloro-5,6-dimethoxyoxepan-3-one 

Relevant academic research and scientific papers

Reconciling solvent effects on rotamer populations in carbohydrates - A joint MD and NMR analysis

The rotational preferences of the hydroxymethyl group in pyranosides is known to depend on the local environment, whether in solid, solution, or gas phase. By combining molecular dynamics (MD) simulations with NMR spectroscopy the rotational preferences for the ω angle in methyl 2,3-di-O-methyl- α-D-glucopyranoside (3) and methyl 2,3-di-O-methyl-α-D- galactopyranoside (6) in a variety of solvents, with polarities ranging from 80 to 2.3 D have been determined. The effects of solvent polarity on intramolecular hydrogen bonding have been identified and quantified. In water, the internal hydrogen bonding networks are disrupted by competition with hydrogen bonds to the solvent. When the internal hydrogen bonds are differentially disrupted, the rotamer populations associated with the ω angle may be altered. In the case of 3 in water, the preferential disruption of the interaction between HO6 and O4 destabilizes the tg rotamer, leading to the observed preference for gauche rotamers. Without the hydrogen bond enhancement offered by a low polarity environment, both 3 and 6 display rotamer populations that are consistent with expectations based on the minimization of repulsive intramolecular oxygen-oxygen interactions. In a low polarity environment, HO6 prefers to interact with O4, however, in water these interactions are markedly weakened, indicating that HO6 acts as a hydrogen bond donor to water.

Establishment of Guidelines for the Control of Glycosylation Reactions and Intermediates by Quantitative Assessment of Reactivity

Stereocontrolled chemical glycosylation remains a major challenge despite vast efforts reported over many decades and so far still mainly relies on trial and error. Now it is shown that the relative reactivity value (RRV) of thioglycosides is an indicator for revealing stereoselectivities according to four types of acceptors. Mechanistic studies show that the reaction is dominated by two distinct intermediates: glycosyl triflates and glycosyl halides from N-halosuccinimide (NXS)/TfOH. The formation of glycosyl halide is highly correlated with the production of α-glycoside. These findings enable glycosylation reactions to be foreseen by using RRVs as an α/β-selectivity indicator and guidelines and rules to be developed for stereocontrolled glycosylation.

Synthesis of MeON-neoglycosides of digoxigenin with 6-deoxy- and 2,6-dideoxy-D-glucose derivatives and their anticancer activity

Cardiac glycosides show anticancer activities and their deoxy-sugar chains are vital for their anticancer effects. In order to study the structure-activity relationship (SAR) of cardiac glycosides toward cancers and get more potent anticancer agents, a series of MeON-neoglycosides of digoxigenin was synthesized and evaluated. First, ten 6-deoxy- and 2,6-dideoxy-D-glucopyranosyl donors were synthesized starting from methyl α-D-glucopyranoside and 2-deoxy-D-glucose. Meanwhile, the digoxigenin was obtained by acidic hydrolysis of commercially available digoxin as glycosyl acceptor. Then, a 22-member MeON-neoglycoside library of digoxigenin was successfully synthesized by neoglycosylation method. Finally, the induction of Nur77 expression and its translocation from the nucleus to cytoplasm together with cytotoxicity of these MeON-neoglycosides were evaluated. The SAR analysis revealed that C3 glycosylation is required for their induction of Nur77 expression. Moreover, some MeON-neoglycosides (2b and 8b) could significant induce the expression of Nur77 and its translocation from the nucleus to cytoplasm. However, these compounds showed no inhibitory effects on the proliferation of cancer cells, suggesting that they may not induce apoptosis of NIH-H460 cancer cells and their underlying potential and application toward cancer cells deserves future study.

Benzylidene Acetal Protecting Group as Carboxylic Acid Surrogate: Synthesis of Functionalized Uronic Acids and Sugar Amino Acids

Direct oxidation of the 4,6-O-benzylidene acetal protecting group to C-6 carboxylic acid has been developed that provides an easy access to a wide range of biologically important and synthetically challenging uronic acid and sugar amino acid derivatives in good yields. The RuCl3-NaIO4-mediated oxidative cleavage method eliminates protection and deprotection steps and the reaction takes place under mild conditions. The dual role of the benzylidene acetal, as a protecting group and source of carboxylic acid, was exploited in the efficient synthesis of six-carbon sialic acid analogues and disaccharides bearing uronic acids, including glycosaminoglycan analogues.

Compositions and methods for modification of biomolecules

The present invention provides modified cycloalkyne compounds; and method of use of such compounds in modifying biomolecules. The present invention features a cycloaddition reaction that can be carried out under physiological conditions. In general, the invention involves reacting a modified cycloalkyne with an azide moiety on a target biomolecule, generating a covalently modified biomolecule. The selectivity of the reaction and its compatibility with aqueous environments provide for its application in vivo (e.g., on the cell surface or intracellularly) and in vitro (e.g., synthesis of peptides and other polymers, production of modified (e.g., labeled) amino acids).

USE OF CO2 FOR THE SYNTHESIS OF CYCLIC GLYCOCARBONATES AND LINEAR POLYGLYCOCARBONATES BY POLYCONDENSATION FROM GLYCANS

Provided herein are methods for synthesizing cyclic carbonates, glycocarbonates, and polyglycocarbonates by reacting polyol glycans with carbon dioxide. Synthesis can include selective polycondensation of polyol glycan hydroxyl moieties.

From d-glucuronic acid to l-iduronic acid derivatives via a radical tandem decarboxylation-cyclization

A synthesis to l-iduronic derivatives, major components of heparin derived pentasaccharides was accomplished by formal inversion of configuration at C-5 of a d-glucuronic acid derivative through radical formation at C-5 using Barton decarboxylation followed by intramolecular radical addition on an acetylenic tether at O-4 giving exclusively a bicyclic sugar of l-ido configuration. Oxidation and ring opening of this bicyclic sugar led to a l-iduronate. This method opens the way to short syntheses of pentasaccharidic moiety of Idraparinux and congeners.

Process of preparation of L-iduronic acid comprising a decarboxylation/intramolecular cyclisation tandem reaction

The present invention relates to a process of preparation of L-iduronic acid and derivatives comprising a decarboxylation/intramolecular cyclisation tandem reaction. The present invention also relates to the intermediates of the process, as well as their use as intermediates in the preparation of Idraparinux.

PROCESS OF PREPARATION OF L-IDURONIC ACID AND DERIVATIVES COMPRISING A DECARBOXYLATION/INTRAMOLECULAR CYCLISATION TANDEM REACTION

The present invention relates to a process of preparation of L-iduronic acid and derivatives comprising a decarboxylation/intramolecular cyclisation tandem reaction. The present invention also relates to the intermediates of the process, as well as their use as intermediates in the preparation of Idraparinux.

Polycarbonates derived from glucose via an organocatalytic approach

An organocatalyzed ring-opening polymerization methodology was developed for the preparation of polycarbonates derived from glucose as a natural product starting material. The cyclic 4,6-carbonate monomer of glucose having the 1, 2, and 3 positions methyl-protected was prepared in three steps from a commercially available glucose derivative, and the structure was confirmed by means of NMR and IR spectroscopies, electrospray ionization mass spectrometry (MS), and single-crystal X-ray analysis. Polymerization of the monomer, initiated by 4-methylbenzyl alcohol in the presence of 1,5,7-triazabicyclo[4.4.0]dec-5-ene as the organocatalyst, proceeded effectively in a controlled fashion to afford the polycarbonate with a tunable degree of polymerization, narrow molecular weight distribution, and well-defined end groups, as confirmed by a combination of NMR spectroscopy, gel-permeation chromatography, and MALDI-TOF MS. A distribution of head-to-head, head-to-tail, and tail-to-tail regiochemistries was determined by NMR spectroscopy and tandem MS analysis by electron transfer dissociation. These polycarbonates are of interest as engineering materials because of their origination from renewable resources combined with their amorphous character and relatively high glass transition temperatures as determined by X-ray diffraction and differential scanning calorimetry studies.