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Influence of protecting groups on O- and C-glycosylation with neuraminyl and ulosonyl dibutylphosphates.

ABSTRACT: The adamantanyl thioglycosides of 5-isothiocyano and 5-azido 5-desamino-4,7,8,9-tetra-O-acetylneuraminic acid methyl ester were converted into the corresponding dibutyl phosphates, which proved to be excellent α-selective donors for O-sialidation with a range of typical acceptors, and good donors for reaction with allyltributylstannane, albeit without significant anomeric selectivity. In the KDN series the dibuylphosphate derived from a donor carrying a 4,5-cyclic carbonate protecting group afforded the corresponding C-glycoside with excellent α-selectivity on activation in the presence of allyltributylstannane, whereas the corresponding donor carrying acetate esters at the 4- and 5-positions was unselective. Overall, it is revealed that while the strongly electron-withdrawing isothiocyanato and azido groups are sufficient to promote highly α-selective O-sialidation, they are inadequate when faced with less reactive nucleophiles when mixtures of anomers are obtained.

SUBMITTER: Ogasahara R

PROVIDER: S-EPMC7484008 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Interplay of Protecting Groups and Side Chain Conformation in Glycopyranosides. Modulation of the Influence of Remote Substituents on Glycosylation?

Project description:The synthesis and conformational analysis of a series of phenyl 2,3,6-tri- O-benzyl-β-d-thio galacto- and glucopyranosides and their 6 S-deuterio isotopomers, with systematic variation of the protecting group at the 4-position, are described. For the galactopyranosides, replacement of a 4- O-benzyl ether by a 4- O-alkanoyl or aroyl ester results in a small but measurable shift in side chain population away from the trans, gauche conformation and in favor of the gauche, trans conformer. In the glucopyranoside series on the other hand, replacement of a 4- O-benzyl ether by a 4- O-alkanoyl or aroyl ester results in a small but measurable increase in the population of the trans, gauche conformer at the expense of the gauche, gauche conformer. The possible modulating effect of these conformational changes on the well-known changes in the anomeric reactivity of glycosyl donors as a function of protecting group is discussed, raising the possibility that larger changes may be observed at the transition state for glycosylation. A comparable study with a series of ethyl 2,3,4-tri- O-benzyl-β-d-thioglucopyranosides reveals that no significant influence in side chain population is observed on changing the O6 protecting group.

| S-EPMC6131524 | biostudies-literature

Automated Glycan Assembly of Oligogalactofuranosides Reveals the Influence of Protecting Groups on Oligosaccharide Stability.

Project description:Galactofurans are an important structural constituent of arabinogalactan and lipopolysaccharides (LPS) ubiquitously present on the envelopes of all Mycobacteria. Key to the automated glycan assembly (AGA) of linear galactofuranosides as long as 20-mers was the identification of thioglycoside building blocks with a fine balance of stereoelectronic and steric effects to ensure the stability of oligogalactofuranoside during the synthesis. A benzoylated galactofuranose thioglycoside building block proved most efficient for oligosaccharide construction.

| S-EPMC8154612 | biostudies-literature

Combinatorial discovery of two-photon photoremovable protecting groups.

Project description:A design principle for a two-photon photochemically removable protecting group based on sequential one-photon processes has been established. The expected performance of such groups in spatially directed photoactivation/photodeprotection has been shown by a kinetic analysis. One particular molecular class fitting into this design, the nitrobenzyl ethers of o-hydroxycinnamates, has been presented. An initial demonstration of two-photon deprotection of one such group prompted further optimization with respect to photochemical deprotection rate. This was accomplished by the preparation and screening of a 135-member indexed combinatorial library. Optimum performance for lambda >350 nm deprotection in organic solvent was found with 4,5-dialkoxy and -cyano substitution in the nitrobenzyl group and 4-methoxy substitution in the cinnamate.

| S-EPMC240653 | biostudies-literature

Isonitrile-responsive and bioorthogonally removable tetrazine protecting groups.

Project description:In vivo compatible reactions have a broad range of possible applications in chemical biology and the pharmaceutical sciences. Here we report tetrazines that can be removed by exposure to isonitriles under very mild conditions. Tetrazylmethyl derivatives are easily accessible protecting groups for amines and phenols. The isonitrile-induced removal is rapid and near-quantitative. Intriguingly, the deprotection is especially effective with (trimethylsilyl)methyl isocyanide, and serum albumin can catalyze the elimination under physiological conditions. NMR and computational studies revealed that an imine-tautomerization step is often rate limiting, and the unexpected cleavage of the Si-C bond accelerates this step in the case with (trimethylsilyl)methyl isocyanide. Tetrazylmethyl-removal is compatible with use on biomacromolecules, in cellular environments, and in living organisms as demonstrated by cytotoxicity experiments and fluorophore-release studies on proteins and in zebrafish embryos. By combining tetrazylmethyl derivatives with previously reported tetrazine-responsive 3-isocyanopropyl groups, it was possible to liberate two fluorophores in vertebrates from a single bioorthogonal reaction. This chemistry will open new opportunities towards applications involving multiplexed release schemes and is a valuable asset to the growing toolbox of bioorthogonal dissociative reactions.

| S-EPMC7012038 | biostudies-literature

Reduction of cysteine-S-protecting groups by triisopropylsilane.

Project description:Triisopropylsilane (TIS), a hindered hydrosilane, has long been utilized as a cation scavenger for the removal of amino acid protecting groups during peptide synthesis. However, its ability to actively remove S-protecting groups by serving as a reductant has largely been mischaracterized by the peptide community. Here, we provide strong evidence that TIS can act as a reducing agent to facilitate the removal of acetamidomethyl (Acm), 4-methoxybenzyl (Mob), and tert-butyl (But ) protecting groups from cysteine (Cys) residues in the presence of trifluoroacetic acid (TFA) at 37 °C. The lability of the Cys protecting groups in TFA/TIS (98/2) in this study are in the order: Cys(Mob) > Cys(Acm) > Cys(But ), with Cys(Mob) being especially labile. Unexpectedly, we found that TIS promoted disulfide formation in addition to aiding in the removal of the protecting group. Our results raise the possibility of using TIS in orthogonal deprotection strategies of Cys-protecting groups following peptide synthesis as TIS can be viewed as a potential deprotection agent instead of merely a scavenger in deprotection cocktails based on our results. We also tested other common scavengers under these reaction conditions and found that thioanisole and triethylsilane were similarly effective as TIS in enhancing deprotection and catalyzing disulfide formation. Our findings reported herein show that careful consideration should be given to the type of scavenger used when it is desirable to preserve the Cys-protecting group. Additional consideration should be given to the concentration of scavenger, temperature of the reaction, and reaction time.

| S-EPMC6773273 | biostudies-literature

Influence of protecting groups on the anomeric equilibrium; case of the 4,6-O-benzylidene acetal in the mannopyranose series.

Project description:It is reported that the replacement of the 4- and 6-O-benzyl ethers in 2,3,4,6-tetra-O-benzyl-?,?-mannopyranose by a 4,6-O-benzylidene acetal results in an increased population of the ?-anomer at equilibrium in CDCl(3) solution. The phenomenon is considered to arise from the lower steric bulk of the benzylidene acetal that, through diminished buttressing interactions, reduces steric interactions normally present in the ?-anomer.

| S-EPMC3396728 | biostudies-literature

Probing the influence of protecting groups on the anomeric equilibrium in sialic acid glycosides with the persistent radical effect.

Project description:A method for the investigation of the influence of protecting groups on the anomeric equilibrium in the sialic acid glycosides has been developed on the basis of the equilibration of O-sialyl hydroxylamines by reversible homolytic scission of the glycosidic bond following the dictates of the Fischer-Ingold persistent radical effect. It is found that a trans-fused 4O,5N-oxazolidinone group stabilizes the equatorial glycoside, i.e., reduces the anomeric effect, when compared to the 4O,5N-diacetyl protected systems. This effect is discussed in terms of the powerful electron-withdrawing nature of the oxazolidinone system, which in turn is a function of its strong dipole moment in the mean plane of the pyranose ring system. The new equilibration method displays a small solvent effect and is most pronounced in less polar media consistent with the anomeric effect in general. The unusual (for anomeric radicals) poor kinetic selectivity of anomeric sialyl radicals is discussed in terms of the planar ?-type structure of these radicals and of competing 1,3-diaxial interactions in the diastereomeric transition states for trapping on the ?- and ?-faces of the radical.

| S-EPMC4004215 | biostudies-literature

Synthesis and Stereocontrolled Equatorially Selective Glycosylation Reactions of a Pseudaminic Acid Donor: Importance of the Side-Chain Conformation and Regioselective Reduction of Azide Protecting Groups.

Project description:Pseudaminic acid is an amino deoxy sialic acid whose glycosides are essential components of many pathogenic Gram-negative bacterial cell walls including those from Pseudomonas aeruginosa, Vibrio cholerae, Campylobacter jejuni, Campylobacter coli, Vibrio vulnificus, and Pseudoalteromonas distincta. The study of pseudaminic acid glycosides is however hampered by poor availability from nature and the paucity of good synthetic methods and limited to no understanding of the factors controlling stereoselectivity. Conformational analysis of the side chains of various stereoisomeric sialic acids suggested that the side chain of pseudaminic acid would take up the most electron-withdrawing trans, gauche-conformation, as opposed to the gauche, gauche conformation of N-acetyl neuraminic acid and the gauche, trans-conformtion of 7- epi N-acetyl neuraminic acid, leading to the prediction of high equatorial selectivity. This prediction is borne out by the synthesis of a suitably protected pseudaminic acid donor from N-acetyl neuraminic acid in 20 steps and 5% overall yield and by the exquisite equatorial selectivity it displays in coupling reactions with typical glycosyl acceptors. The selectivity of the glycosylation reactions is further buttressed by the development and implementation of conditions for the regioselective release of the two amines from the corresponding azides, such as required for the preparation of the lipopolysaccharides. These findings open the way to the synthesis and study of pseudaminic acid-based bacterial lipopolysaccharides and, importantly in the broader context of glycosylation reactions in general, underline the significant role played by side-chain conformation in the control of reactivity and selectivity.

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Quantum Dot-Catalyzed Photoreductive Removal of Sulfonyl-Based Protecting Groups.

Project description:This Communication describes the use of CuInS2 /ZnS quantum dots (QDs) as photocatalysts for the reductive deprotection of aryl sulfonyl-protected phenols. For a series of aryl sulfonates with electron-withdrawing substituents, the rate of deprotection for the corresponding phenyl aryl sulfonates increases with decreasing electrochemical potential for the two electron transfers within the catalytic cycle. The rate of deprotection for a substrate that contains a carboxylic acid, a known QD-binding group, is accelerated by more than a factor of ten from that expected from the electrochemical potential for the transformation, a result that suggests that formation of metastable electron donor-acceptor complexes provides a significant kinetic advantage. This deprotection method does not perturb the common NHBoc or toluenesulfonyl protecting groups and, as demonstrated with an estrone substrate, does not perturb proximate ketones, which are generally vulnerable to many chemical reduction methods used for this class of reactions.

| S-EPMC7480491 | biostudies-literature

Sensitive Oligodeoxynucleotide Synthesis Using Dim and Dmoc as Protecting Groups.

Project description:In traditional oligodeoxynucleotide (ODN) synthesis, phosphate groups are protected with the 2-cyanoethyl group, and amino groups are protected with acyl groups. At the end of ODN synthesis, deprotection is achieved with strong bases and nucleophiles. Therefore, traditional technologies are not suitable for the synthesis of ODNs containing sensitive functionalities. To address the problem, we report the use of Dim and Dmoc groups, which are based on the 1,3-dithian-2-yl-methyl function, for phosphate and amine protection for the solid phase ODN synthesis. Using the new Dim-Dmoc protection, deprotection was achieved under mild oxidative conditions without using any strong bases and nucleophiles. As a result, the new technology is suitable for the synthesis of ODNs containing sensitive functions. To demonstrate feasibility, seven 20-mer ODNs including four that contain sensitive ester and alkyl chloride groups were synthesized, purified with RP HPLC, and characterized with MALDI-TOF MS and enzyme digestion essays. High purity ODNs were obtained.

| S-EPMC6825528 | biostudies-literature

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