3013-58-9

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 
• 50-99-7 D-glucose 
• 1125-88-8 benzaldehyde dimethyl acetal 
• 97-30-3 methyl-alpha-D-glucopyranoside 
• 64552-06-3 methyl 4,6-O-benzylidene-α-D-galactopyranoside 
• 59-23-4 D-Galactose 
• 3396-99-4 methyl 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 
• 106220-89-7 methyl 6-O-benzyl-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 
• 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 
• 1384974-98-4 (4S,5R,6S)-4-benzyloxy-5,6-dimethoxyoxepan-3-one 

Relevant academic research and scientific papers

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.

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).

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.

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.

Probing the influence of a 4,6-O-acetal on the reactivity of galactopyranosyl donors: Verification of the disarming influence of the trans-gauche conformation of C5-C6 bonds

The effect of a 4,6-O-alkylidene acetal on the rate of acid-catalyzed hydrolysis of methyl galactopyranosides and of spontaneous hydrolysis of 2,4-dinitrophenyl galactopyranosides has been studied through the synthesis and hydrolysis of analogs in which O6 is replaced by a methoxymethylene unit in which the methoxy group adopts either an equatorial or an axial position according to the configuration. Consistent with earlier studies under both acid-catalyzed and spontaneous hydrolysis conditions, the alkylidene acetal, or its 7-carba analog, retards hydrolysis with respect to comparable systems lacking the cyclic protecting group. The configuration at C6 in the 7-carba analogs does not influence the rate of acid-catalyzed hydrolysis but has a minor influence on the rate of spontaneous hydrolysis of the 2,4-dinitrophenyl galactosides, confirming earlier studies on the role played by the hydroxymethyl group conformation on glycoside reactivity. The benzylidene acetal is found to stabilize the α-anomer of galactopyranose derivatives relative to monocyclic analogs. Reasons for the α-selectivity of 4,6-O-benzylidene- protected galactopyranosyl donors bearing neighboring group-active protecting groups at O2 are discussed.

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.

Poly(d-glucose carbonate) block copolymers: A platform for natural product-based nanomaterials with solvothermatic characteristics

A natural product-based polymer platform, having the characteristics of being derived from renewable materials and capable of breaking down, ultimately, into natural byproducts, has been prepared through the ring-opening polymerization (ROP) of a glucose-based bicyclic carbonate monomer. ROP was carried out via chain extension of a polyphosphoester (PPE) macroinitiator in the presence of 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) organocatalyst to afford the PPE-b-poly(d-glucose carbonate) (PDGC) block copolymer. This new copolymer represents a functional architecture that can be rapidly transformed through thiol-yne reactions along the PPE segment into a diverse variety of amphiphilic polymers, which interestingly display stimuli-sensitive phase behavior in the form of a lower critical solution temperature (LCST). Below the LCST, they undergo self-assembly to form spherical core-shell nanostructures that display a poorly defined core-shell morphology. It is expected that hydrophobic patches are exposed within the micellar corona, reminiscent of the surface complexity of proteins, making these materials of interest for triggered and reversible assembly disassembly processes.