65556-00-5

Upstream product

• 98-59-9 p-toluenesulfonyl chloride 
• 3162-96-7 4,6-O-benzylidene-1-O-methyl-α-D-glucopyranoside 
• 50-99-7 D-glucose 
• 71117-36-7 methyl 4,6-O-(S)-benzylidene-β-D-galactopyranoside 
• 1824-94-8 methyl beta-D-galactopyranoside 
• 28538-12-7 methyl 2-O-benzoyl-4,6-O-benzylidene-3-O-p-tolylsulfonyl-α-D-allopyranoside 
• 6698-34-6 methyl 4,6-O-benzylidene-3-O-p-tolylsulfonyl-α-D-allopyranoside 
• 1125-88-8 benzaldehyde dimethyl acetal 
• 100-52-7 benzaldehyde 
• 97-30-3 methyl-alpha-D-glucopyranoside 

Downstream Products

• 66674-15-5 methyl 4,6-O-benzylidene-3-O-(p-tolylsulfonyl)-α-D-glucopyranoside 
• 66537-92-6 methyl 2,3-anhydro-4,6-benzylidene-α-D-allopyranoside 
• 6972-98-1 methyl-[O⁴,O⁶-((R)-ethylidene)-O²,O³-bis-(toluene-4-sulfonyl)-α-D-glucopyranoside] 
• 102219-87-4 methyl 4-O-<(S)-cyanophenylmethyl>-2,3-di-O-tosyl-α-D-glucopyranoside 
• 102243-10-7 methyl 6-O-<(R)-cyanophenylmethyl>-2,3-di-O-tosyl-α-D-glucopyranoside 
• 65530-27-0 (2R,4aR,6S,8aS)-(+)-6-methoxy-2-phenyl-4,4a,6,8a-tetrahydropyrano[3,2-d][1,3]dioxine 
• 120123-51-5 methyl 6-O-benzoyl-2,3-di-O-tosyl-α-D-glucopyranoside 
• 56607-37-5 methyl 4-O-benzoyl-2,3-di-O-tosyl-α-D-glucopyranoside 
• 65530-28-1 methyl 4,6-O-benzylidene-3-deoxy-α-D-glucopyranoside 
• 6752-48-3 methyl 4,6-O-benzylidene-2-deoxy-α-D-glucopyranoside 
• 116809-48-4 methyl 4-O-benzoyl-2,3-di-O-toluene-p-sulfonyl-6-deoxy-α-D-glucopyranoside 
• 107908-97-4 methyl 2,6-dideoxy-3-O-benzyl-α-D-lyxo-hexopyranoside 
• 90762-83-7 Methyl 3-O-benzyl-2,6-dideoxy-α-D-arabino-hexopyranoside 
• 128537-00-8 methyl 2-O-benzyl-3,6-dideoxy-α-D-ribo-hexopyranoside 

Relevant academic research and scientific papers

A Domino Epoxide Ring-Opening Xanthate Migration Reaction: An Alternative Entry to Thiosugars

A sterereospecific and efficient synthesis of thiosugars derived from levoglucosenone and methyl α-d-glucopyranoside was developed by a domino epoxide ring opening- xanthate migration to afford 1,3-oxathiolane-2-thiones in high yields. The stereochemical outcome of the new C–S bond was defined by the configuration of the starting materials. The 1,3-oxathiolane-2-thiones were subsequently submitted to a second tandem reaction affording the corresponding 2,3-episulfide alcohols. The thiosugars obtained are useful building blocks for the synthesis of thiooligosaccharides with potential biological properties.

Hybridisation potential of 1′,3′-Di-O-methylaltropyranoside nucleic acids

In further study of our series of six-membered ring-containing nucleic acids, different 1′,3′-di-O-methyl altropyranoside nucleoside analogs (DMANA) were synthesized comprising all four base moieties, adenine, cytosine, uracil and guanine. Following assembly into oligonucleotides (ONs), their affinity for natural oligonucleotides was evaluated by thermal denaturation of the respective duplexes. Data were compared with results obtained previously for both anhydrohexitol (HNAs) and 3′-O-methylated altrohexitol modified ONs (MANAs). We hereby demonstrate that ONs modified with DMANA monomers, unlike some of our previously described analogues with constrained 6-membered hexitol rings, did not improve thermodynamic stability of dsRNA complexes, most probably in view of an energetic penalty when forced in the required 1C4 pairing conformation. Overall, a single incorporation was more or less tolerated or even positive for the adenine congener, but incorporation of a second modification afforded a slight destabilization (except for A), while a fully modified sequence displayed a thermal stability of -0.3°C per modification. The selectivity of pairing remained very high, and the new modification upon incorporation into a DNA strand, strongly destabilized the corresponding DNA duplexes. Unfortunately, this new modification does not bring any advantage to be further evaluated for antisense or siRNA applications.

α- and β-Lipomycin: Total syntheses by sequential stille couplings and assignment of the absolute configuration of all stereogenic centers

40 years ago spectroscopy, derivatization, and degradation revealed the structures of α-lipomycin and its aglycon β-lipomycin except for the configurations of their side-chain stereocenters. We synthesized all relevant β-lipomycin candidates: the (12R,13S

Evidence of cation-coordination involvement in directing the regioselective di-inversion reaction of vicinal di-sulfonate esters

Direct evidence has been obtained to confirm the unusual nucleophilic attack of an alkoxide at the S-center of sp3-hybridized sulfonyl esters. The unusual reaction pathway leads to S-O bond scission which is crucial for the regio- and stereoselective conversion of 2,3-di-O-sulfonates of 4,6-O-benzylidene-β-d-galactopyranosides into β-d-idopyranosides. In addition, strong evidence has been provided to clarify the role of the alkali counter-cation in the transformation. The cation is believed to influence the reaction rate via coordination to an oxygen in the sulfonate ester; the presence of a neighboring ring oxygen oriented in a cis-relationship greatly enhances reactivity of the sulfonyl ester.

A scalable approach to obtaining orthogonally protected β-d-idopyranosides

A practical method to obtain orthogonally protected d-idopyranose from d-galactose has been developed, which is the first method to enable synthesis of the challenging β-d-idopyranoside linkage. The method relies on a key double inversion at O-2 and O-3 in an easily prepared d-galactose derivative, which proceeds regio- and stereoselectively through a 2,3-anhydrotalopyranoside; reaction using a selection of alkoxides affords exclusively the 3-O-alkylidopyranoside, which can be used to generate an orthogonally protected monosaccharide. The process is scalable and requires minimal purification, so it could be used to produce building blocks to aid in the synthesis of various β-idopyranose-containing oligosaccharide targets to further probe their biological functions.

Synthesis of locked pyranosyl nucleic acid (LpNA)

A new locked pyranosyl nucleoside was synthesized by phenylsulfinyl- assisted chemistry. The novel building block was inserted into oligonucleotides and provides new insight on conformational restricted pyranosyl nucleosides on duplex formation

Assembly of digitoxin by gold(I)-catalyzed glycosidation of glycosyl o-alkynylbenzoates

Digitoxin, a clinically important cardiac trisaccharide, was assembled efficiently from digitoxigenin and 3,4-di-O-tert-butyldiphenylsilyl-d- digitoxosyl o-cyclopropylethynylbenzoate in 9 steps and 52% overall yield via alternate glycosylation and protecting group manipulation. The present synthesis showcases the advantage of the gold(I)-catalyzed glycosylation protocol in the synthesis of glycoconjugates containing acid-labile 2-deoxysugar linkages.

Enantioselective synthesis of phyllanthurinolactone, a leaf-closing substance of Phyllanthus urinaria L., and its analogs toward the development of molecular probes

We report enantioselective synthesis of phyllanthurinolactone (1), a leaf-closing substance of Phyllanthus urinaria L., and its analogs with sugars other than D-glucose. Structure-activity relationship study using them revealed that the structure of the sugar moiety did not affect their bioactivity at all. This result is very important for the development of molecular probes based on the structure of 1.

Novel and convenient method for the syntheses of 2,6-dideoxypyranoses, 3,6-dideoxypyranoses, and azido (amino) analogs of 3,6-dideoxypyranoses

A novel method of regioselective deoxygenation of methyl 4,6-O-benzylidene-2,3-di-O-tosyl-α-D-glucopyranoside, and its application for the syntheses of 2,6-dideoxypyranoses, 3,6-dideoxypyranoses, and azido (amino) analogs of 3,6-dideoxypyranoses were reported.

Stereochemical dependence of the mechanism of deoxygenation, with lithium triethylborohydride, in 4,6-O-benzylidenehexopyranoside p-toluenesulfonates

Lithium triethylborohydride was shown to react with methyl 4,6-O-benzylidene-α-D-hexopyranoside 2- and 3-tosylates, and 2,3-ditosylates, in the manno, allo, and altro configurational series both by O-S fission (O-desulfonylation) and by C-O fission (C-desulfonyloxylation), to produce carbinol and deoxy functions, respectively.The results were compared with those previously obtained with the corresponding gluco and galacto isomers, and the degree of facility of the cleavage reactions was seen to depend on the position of the sulfonic ester groups and the overall configuration of the molecules.The mechanism of reductive desulfonyloxylation also depended on configuration and was demonstrated to involve intermediary epoxide formation or displacement by internal hydride shift as the principal paths; competing elimination and direct nucleophilic displacement were found to occur in the allo series, whereas reduction accompanied by ring contraction has thus far been encountered only in the conformationally less constrained, cis-fused acetal system of the galacto series.Like the borohydride reagent, lithium aluminum hydride was found to react (though much more slowly) with the altro 2,3-ditosylate by the epoxide-mediated mechanism, although the latter hydride is known to desulfonyloxylate the α-D-gluco-isomer by a different, intramolecular reduction mechanism.