187880-20-2

Upstream product

• 2186-92-7 p-Anisaldehyde dimethyl acetal 
• 2873-29-2 D-glucal triacetate 
• 13265-84-4 D-glucal 
• 273749-60-3 phenyl 4,6-O-(4-methoxybenzylidene)-1-thio-β-D-glucopyranoside 

Downstream Products

• 187879-14-7 4,6-O-(4-methoxybenzylidene)-3-O-(triisopropyl)silyl-D-(-)-glucal 
• 199116-19-3 C₈₀H₁₀₂O₁₅Si₂ 
• 199116-18-2 4-O-(4-methoxybenzyl)-3-O-(triisopropyl)silyl-D-glucal 
• 629652-46-6 4,6-di-O-(4-methoxybenzyl)-2-deoxy-α,β-D-glucopyranose 
• 629652-48-8 2-deoxy-4,6-di-O-(4-methoxybenzyl)-D-gluco-γ-lactone 
• 629652-49-9 2-deoxy-1,3-dioxo-4,6-di-O-(4-methoxybenzyl)-D-(+)-glucopyranose 
• 629652-41-1 4,6-di-O-(4-methoxybenzyl)-3-O-(triisopropyl)silyl-D-(-)-glucal 
• 629652-43-3 4,6-di-O-(4-methoxybenzyl)-2-deoxy-3-O-(triisopropyl)silyl-α,β-D-glucopyranose 

Relevant academic research and scientific papers

CARBOCYCLIC DERIVATIVES AND CONJUGATED DERIVATIVES THEREOF, AND THEIR USE IN VACCINES

The invention is in the field of vaccines and relates to oligomers having a selected degree of polymerization, obtained by connecting together a number of carbocyclic repeating units, and to conjugated derivatives thereof. The oligomers and conjugated derivatives thereof of the invention also have a selected degree of acetylation. The derivatives of the invention are useful for the preparation of immunogenic compositions, e.g. in the form of a vaccine.

Reagent-Controlled Divergent Synthesis of C-Glycosides

By turning on or switching off the directing effect of the C3-OH-located o-diphenylphosphanylbenzoyl (o-DPPB) group in glycals, a reagent-controlled protocol for divergent and regio- and stereoselective syntheses of C-glycosides has been established. In particular, the silence of the directing effect of o-DPPB was achieved by the introduction of a ZnCl2 additive, which is operationally simple and efficient. The flexibility of the novel protocol was exhibited not only by the easy access of both α- and β-C-glycosides but also by the versatility of the obtained formal Ferrier rearrangement products, which can be easily derivatized to various C-glycoside analogues owing to the embedded multifunctionalities.

Synthesis of (-)-morphine: Application of sequential claisen/claisen rearrangement of an allylic vicinal diol

A detailed exploration of the synthesis of (-)-morphine based on sequential [3,3]-sigmatropic rearrangements is described. The sequential Claisen/Claisen rearrangements of an allylic vicinal diol resulted in the stereoselective formation of the two contiguous carbon centers, including a sterically encumbered quaternary carbon, in a single operation. The two ethyl esters generated in this reaction were successfully differentiated during a subsequent Friedel-Crafts-type cyclization. The (-)-morphine double bond was introduced at a late stage in our first-generation synthesis, but was formed at an earlier stage in the second-generation synthesis, resulting in a more efficient route to the end product.

Conformational domino effect in saccharides: A prediction from alkyl β-(1→6)-diglucopyranosides

(Chemical Equation Presented) A series of alkyl β-D-glucopyranosyl- (1→6)-β-D-glucopyranosides, containing nonchiral and chiral aglycons, were synthesized and analyzed by NMR and CD. The results, collected from four sets of disaccharides, demonstrated that the rotational properties of the interglycosidic linkage depend on the structural natures of both the aglycon and the solvent. Stereoelectronic and steric factors explain this rotational dependence, the gauche-trans (gt) rotamer being the most stable. Furthermore, correlations between Taft's steric parameters or between the pKa values of the alkyl substituent (aglycon) versus corresponding rotamer populations were observed. These results point to a natural conformational domino effect in oligosaccharides, where the conformational properties of each (1→6) interglycosidic linkage will depend on the structure of the previous residue or its aglycon. In addition, a very weak rotational population dependence of the hydroxymethyl group at residue II on the aglycon at residue I was observed. The population of the gauche-gauche (gg) rotamer decreased, and that of gt increased as the Taft's steric parameters of the remote aglycon increased, independently of the disaccharide series and of the solvent.

Formal synthesis of (-)-morphine from d-glucal based on the cascade Claisen rearrangement

The formal synthesis of (-)-morphine is described. The C-ring in morphine was prepared in an optically pure form from d-glucal using Ferrier's carbocyclization reaction, and the vicinal tertiary and quaternary stereocenters in the C-ring were stereoselect

A highly convergent synthesis of an N-linked glycopeptide presenting the H-type 2 human blood group determinant

The total synthesis of an H-type blood group determinant in a model biological setting is described. The construct is comprised of a high mannose core structure with projecting lactose spacers, culminating in a two-copy presentation of the H-type blood group determinant itself. Key reactions that were used in this construction include sulfonamidohydroxylation (see 15→18) and benzoate-directed glycosylation via an activated thiophenyl donor (see 34→36). Another key strategic element involved the epimerization of an interior core glucoside to reach the β-mannoside (see 37→38) required in the ring C sugar of the high mannose core.

Totally Stereoselective Synthesis of 1,3-Disaccharides through Diels-Alder Reactions

A nonclassical, totally stereoselective synthesis of orthogonally protected 1,3-disaccharides is reported. Enantiomerically pure β-keto-δ-lactones, efficiently obtained from glucal and galactal, are transformed into electron-poor heterodienes and chemo-,

Synthesis and transformations of D-glucuronic and L-iduronic acid glycals

D-Glucuronic acid glycals can be efficiently synthesized from diacetone glucose or tri-O-acetyl glycal and can be transformed into D-glucuronic acid donors and acceptors in high yields. Base catalyzed epimerization of D-glucuronic acid glycals provides access to the corresponding L-iduronic acid glycals. Both D-glucuronic and L-iduronic acid glycals were transformed into glycosylating agents for use in the synthesis of glycosaminoglycan oligosaccharides.

Stereoselective synthesis of [13C]methyl 2-[15N]amino-2-deoxy-beta-D-glucopyranoside derivatives.

Efficient syntheses of three [13C]methyl 2-[15N]amino-2-deoxy-beta-D-glucopyranoside derivatives are described. Amination of the D-glucal with (saltmen)Mn(15N) proceeded with 11:1 stereoselectivity favoring the gluco configuration; subsequent methylation of the [15N]lactol using [13C]iodomethane and silver(I) oxide afforded the doubly labeled beta glucoside in high yield. This compound served as the common precursor for three [13C]methyl 2-[15N]aminoglucosides: (2-[15N]trifluoroacetyl-), (2-[15N]acetyl-), and (2-[15N]azido-). Selected heteronuclear coupling constants are reported.

A highly convergent total synthetic route to glycopeptides carrying a high-mannose core pentasaccharide domain N-linked to a natural peptide motif

N-Linked glycopeptides were synthesized by condensation of a high-mannose anomeric amine bearing a pentasaccharide with aspartic-acid-containing tri- and pentapeptides through the agency of IIDQ. The pentasaccharide portion, corresponding to the 'core' re