167074-37-5

Upstream product

• 74-96-4 ethyl bromide 
• 19465-09-9 methyl 4,6-O-benzylidene-2-bromo-2-deoxy-α-D-altropyranoside 
• 3150-15-0 methyl 2,3-anhydro-4,6-O-benzylidene-α-D-allopyranoside 
• 557-18-6 diethylmagnesium 
• 925-90-6 ethylmagnesium bromide 
• 4416-59-5 n-decyllithium 
• 14125-73-6 Methyl-4,6-O-benzyliden-2-deoxy-2-jod-α-D-altropyranosid 
• 134756-58-4 C₁₉H₁₈O₃S 
• 111425-52-6 thiophenyl 2,3-dideoxy-α-D-glucopyranoside 
• 111425-49-1 phenyl 4,6-di-O-acetyl-2,3-dideoxy-1-thio-α-D-erythro-hex-2-enopyranoside 
• 69534-73-2 3,4,6-O-tri-O-acetyl-D-glucal 
• 67-56-1 methanol 
• 63598-38-9 1,5-anhydro-4,6-O-benzylidene-2-deoxy-D-ribo-hex-1-enopyranose 
• 98-88-4 benzoyl chloride 

Downstream Products

• 7226-39-3 2-deoxy-2-fluoro-D-mannopyranose 
• 38711-37-4 2-deoxy-2-fluoro-β-D-glucopyranose 
• 7226-39-3 2-fluoro-2-deoxy-D-glucose 
• 55449-80-4 2-deoxy-2-fluoro-β-D-mannopyranose 
• 63598-38-9 1,5-anhydro-4,6-O-benzylidene-2-deoxy-D-ribo-hex-1-enopyranose 

Relevant academic research and scientific papers

A new entry to 4,6-O-benzylidene glucal from phenyl 1-seleno-α-d- mannopyranoside

The two-step synthesis of 4,6-O-benzylidene glucal, in 59% overall yield, from phenyl 1-seleno-α-d-mannopyranoside is described.

Synthetic heparin pentasaccharides

Preparation and use of synthetic monosaccharides, disaccharides, trisaccharides, tetrasaccharides and pentasaccharides useful for the preparation of synthetic heparinoids.

A robust synthesis of N-glycolyl muramyl dipeptide via azidonitration/reduction

A novel synthetic route leading to N-glycolyl muramyl dipeptide (MDP), a bacterial glycopeptide of particular interest in studies of nucleotide-binding oligomerization domain-containing protein 2 (NOD2), is described. The synthetic strategy hinges on the alkylation of benzylidene-protected glucal with 2-bromopropionic acid and thus circumvents a challenging and non-reproducible SN2 step at the C-3 position of glucosamine derivatives. The subsequent sequence includes an azidonitration and an unusual azide reduction/acylation step via an aza ylide/oxaphospholidine intermediate. This approach generates a protected N-glycolyl MDP that can be either subjected to a one-step global deprotection or differentially deprotected to obtain further derivatives.

A 3,4-trans-fused cyclic protecting group facilitates α-selective catalytic synthesis of 2-deoxyglycosides

A practical approach has been developed to convert glucals and rhamnals into disaccharides or glycoconjugates with high α-selectivity and yields (77-97 %) using a trans-fused cyclic 3,4-O-disiloxane protecting group and TsOH·H2O (1 mol %) as a catalyst. Control of the anomeric selectivity arises from conformational locking of the intermediate oxacarbenium cation. Glucals outperform rhamnals because the C6 side-chain conformation augments the selectivity.

Epimerization of glycal derivatives by a cyclopentadienylruthenium catalyst: Application to metalloenzymatic DYKAT

Epimerization of a non-anomeric stereogenic center in carbohydrates is an important transformation in the synthesis of natural products. In this study an epimerization procedure of the allylic alcohols of glycals by cyclopentadienylruthenium catalyst 1 is presented. The epimerization of 4,6-O-benzylidene-d-glucal 4 in toluene is rapid, and an equlibrium with its d-allal epimer 5 is established within 5 min at room temperature. Exchange rates for allal and glucal formation were determined by 1D 1H EXSY NMR experiments to be 0.055 s-1 and 0.075 s -1, respectively. For 4-O-benzyl-l-rhamnal 8 the epimerization was less rapid and four days of epimerization was required to achieve equilibration of the epimers at room temperature. The epimerization methodology was subsequently combined with acylating enzymes in a dynamic kinetic asymmetric transformation (DYKAT), giving stereoselective acylation to the desired stereoisomers 12, 13 , and 15. The net effect of this process is an inversion of a stereogenic center on the glycal, and yields ranging from 71% to 83% of the epimer were obtained.

Stereoelectronic factors in the stereoselective epoxidation of glycals and 4-deoxypentenosides

Glycals and 4-deoxypentenosides (4-DPs), unsaturated pyranosides with similar structures and reactivity profiles, can exhibit a high degree of stereoselectivity upon epoxidation with dimethyldioxirane (DMDO). In most cases, the glycals and their corresponding 4-DP isosteres share the same facioselectivity, implying that the pyran substituents are largely responsible for the stereodirecting effect. Fully substituted dihydropyrans are subject to a "majority rule", in which the epoxidation is directed toward the face opposite to two of the three groups. Removing one of the substituents has a variable effect on the epoxidation outcome, depending on its position and also on the relative stereochemistry of the remaining two groups. Overall, we observe that the greatest loss in facioselectivity for glycals and 4-DPs is caused by removal of the C3 oxygen, followed by the C5/anomeric substituent, and least of all by the C4/C2 oxygen. DFT calculations based on polarized-π frontier molecular orbital (PPFMO) theory support a stereoelectronic role for the oxygen substituents in 4-DP facioselectivity, but less clearly so in the case of glycals. We conclude that the anomeric oxygen in 4-DPs contributes toward a stereoelectronic bias in facioselectivity whereas the C5 alkoxymethyl in glycals imparts a steric bias, which at times can compete with the stereodirecting effects from the other oxygen substituents.

A facile synthesis of 4,6-O-benzylidene-d-glycals via 1,5-anhydro-4,6-O-benzylidene-d-hex-1-en-3-ulose

Benzylidenation of readily available 1,5-anhydro-d-hex-1-en-3-ulose, followed by sodium borohydride reduction, afforded the title compounds in high yields. Separation of 4,6-O-benzylidene-d-allal and -d-glucal was accomplished by selective acetylation wit

Synthesis of saponins with cholestanol, cholesterol, and friedelanol as aglycones

Procedures for the synthesis of branched Xylss(1→3)[Galss- (1→2)]-Glc and Xylss(1→3)[Galss(1→2)]-GlcUA trisaccharides ss-linked to the 3-O of cholesterol, cholestanol, and friedelanol, respectively, were developed. To this end, ss-selective glucosylation

A facile synthesis of 4,6-O-benzylidene glucal

4,6-O-Benzylidene protected D-glucal, a useful synthetic intermediate, may be accessed from the extremely cheap and readily available starting material α-methyl glucopyranoside, via a simple four-step reaction sequence involving selective triflation and iodide displacement at C-2.

Stereoselective synthesis of a C-glycosylic compound (a "methyl C-glycoside") through a regioselective free-radical ring-opening reaction. A single-crystal X-ray structure determination

Readily available 3,4,6-tri-O-acetyl-D-glucal was converted to 2,6-anhydro-5,7-O-benzylidene-1,3,4-trideoxy-D-arabino-hept-3-enitol, a methyl C-glycosylic compound. Cyclopropanation of 4,6-O-benzylidene-D-glucal, followed by tributylstannyl radical-mediated regioselective ring opening of the 1,2-cyclopropano sugar led to a 2,6-anhydro-1-deoxyheptose, (a "methyl C-β-D-glycoside"). The stereochemistry of the 1,2-cyclopropano sugar and the "methyl C-glycoside" were confirmed by single-crystal X-ray diffraction studies.