126641-47-2

Upstream product

• 83-87-4 β-D-mannopyranose pentaacetate 
• 3947-62-4 2,3,4,6-tetra-O-acetyl-D-mannopyranose 
• 13992-16-0 phenyl 2,3,4,6-tetra-O-acetyl-1-thio-α-D-mannopyranoside 
• 65236-85-3 β-1-deoxy-1-C-(phenylthio)-2,3,4,5-tetra-O-acetyl-D-mannopyranose 
• 13242-53-0 acetobromomannose 
• 66888-27-5 penta-O-acetyl-D-mannose 
• 65785-54-8 1-fluoro-2-methyl-N,N-diisopropyl-propenylamine 
• 83-87-4 D-Mannose pentaacetate 
• 211801-79-5 4-methylphenyl 2,3,4,6-tetra-O-acetyl-1-thio-α-D-mannopyranoside 
• 4163-65-9 per-O-acetyl-α-D-mannopyranose 
• 3458-28-4 D-Mannose 
• 108-24-7 acetic anhydride 
• 22860-22-6 2,3,4,6-tetra-O-acetyl-α-D-mannopyranose 
• 572-09-8 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl bromide 

Downstream Products

• 148806-97-7 N^α-fluoren-9-ylmethoxycarbonyl-O-(2,3,4,6-tetra-O-acetyl-α-D-mannopyranosyl)-L-threonine benzyl ester 
• 439-01-0 2,3,4,6-tetra-O-benzoyl-α-D-mannopyranosyl fluoride 
• 28541-77-7 4-bromophenyl α-D-mannopyranoside 
• 187269-63-2 2,3,4,6-tetra-O-pivaloyl-α-D-mannopyranosyl fluoride 
• 243120-93-6 4-bromophenyl tetra-O-pivaloyl-α-D-mannopyranoside 
• 243120-94-7 4-nitrobenzyl tetra-O-pivaloyl-α-D-mannopyranoside 
• 117894-99-2 methyl (2,3,4,6-tetra-O-benzyl-α-D-mannopyranosyl)-(1→4)-2,3,6-tri-O-benzyl-α-D-glucopyranoside 
• 78153-79-4 2,3,4,6-tetra-O-benzyl-α-D-mannopyranosyl fluoride 

Relevant academic research and scientific papers

A Concise Method for the Preparation of Glycosyl Fluorides via Displacement Reactions of 1-Arylthioglycosides with 4-Methyl(difluoroiodo)benzene

A variety of usefully functionalised 1-fluoroglycosides may be prepared under mild conditions from their corresponding arylthioglycoside derivatives by reaction with 4-methyl(difluoroiodo)benzene.

PREPARATION OF GLYCOSYL HALIDES UNDER NEUTRAL CONDITIONS

The anomeric hydroxyl group of various furanose and pyranose hemiacetals can be replaced by a fluorine, chlorine, bromine or iodine atom under neutral conditions using haloenamines.

Preparation of 1-fluoroglycosides from 1-arylthio and 1-arylselenoglycosides using 4-methyl(difluoroiodo)benzene

Treatment of readily available thio- and selenoglycosides with the reagent 4-methyl(difluoroiodo)benzene leads to the formation of the corresponding fluoroglycosides in moderate to good yield.

Glycosynthases from Thermotoga neapolitana β-glucosidase 1A: A comparison of α-glucosyl fluoride and in situ-generated α-glycosyl formate donors

TnBgl1A from the thermophile Thermotoga neapolitana is a dimeric β-glucosidase that belongs to glycoside hydrolase family 1 (GH1), with hydrolytic activity through the retaining mechanism, and a broad substrate specificity acting on β-1,4-, β-1,3- and β-1,6-linkages over a range of glyco-oligosaccharides. Three variants of the enzyme (TnBgl1A-E349G, TnBgl1A-E349A and TnBgl1A-E349S), mutated at the catalytic nucleophile, were constructed to evaluate their glycosynthase activity towards oligosaccharide synthesis. Two approaches were used for the synthesis reactions, both of which utilized 4-nitrophenyl β-d-glucopyranoside (4NPGlc) as an acceptor molecule: the first using an α-glucosyl fluoride donor at low temperature (35 °C) in a classical glycosynthase reaction, and the second by in situ generation of the glycosyl donor with (4NPGlc), where formate served as the exogenous nucleophile under higher temperature (70 °C). Using the first approach, TnBgl1A-E349G and TnBgl1A-E349A synthesized disaccharides with β-1,3-linkages in good yields (up to 61%) after long incubations (15 h). However, the GH1 glycosynthase Bgl3-E383A from a mesophilic Streptomyces sp., used as reference enzyme, generated a higher yield at the same temperature with both a shorter reaction time and a lower enzyme concentration. The second approach yielded disaccharides for all three mutants with predominantly β-1,3-linkages (up to 45%) but also β-1,4-linkages (up to 12.5%), after 7 h reaction time. The TnBgl1A glycosynthases were also used for glycosylation of flavonoids, using the two described approaches. Quercetin-3-glycoside was tested as an acceptor molecule and the resultant product was quercetin-3,4′-diglycosides in significantly lower yields, indicating that TnBgl1A preferentially selects 4NPGlc as the acceptor.

The reaction coordinate of a bacterial GH47 α-mannosidase: A combined quantum mechanical and structural approach

Mannosides in the southern hemisphere: Conformational analysis of enzymatic mannoside hydrolysis informs strategies for enzyme inhibition and inspires solutions to mannoside synthesis. Atomic resolution structures along the reaction coordinate of an inverting α-mannosidase show how the enzyme distorts the substrate and transition state. QM/MM calculations reveal how the free energy landscape of isolated α-D-mannose is molded on enzyme to only allow one conformationally accessible reaction coordinate. Copyright

Organofluorine compounds and fluorinating agents; 18. Trifluoromethylzinc bromide as a reagent for the preparation of glycosyl fluorides

Trifluoromethylzinc bromide was used to prepare the corresponding glycosyl fluorides from the peracetylated α-pyranosyl bromides of D-glucose 1, D-galactose 3, D-mannose 5, D-lyxose 7, and L-rhamnose 9, respectively, in good yields. D-Glucopyranosyl bromide 1 and the D-galactopyranosyl bromide 3, exclusively delivered the corresponding β-D-glycosyl fluorides 2β and 4β. The other bromides 5, 7 and 9 formed mixtures of anomeric fluorides (6α/6β, 8α/8β, 10α/10β). Similarily, the anomeric OH-groups of the D-glycopyranoses 11, 12, 13, 15, 17 could be substituted by fluoride using trifluoromethylzinc bromide/titanium tetrafluoride. In all cases mixtures of anomeric fluorides 2α/2β, 6α/6β, 14α/14β, 16α/16β, and 18α/18β were obtained.

Simultaneous detection of different glycosidase activities by 19F NMR spectroscopy

A fast method for the simultaneous detection of different glycosidolytic activities in commercially available enzyme preparations and crude culture filtrates was found in using, as substrate, a mixture of different glycosyl fluorides and 19F NMR spectroscopy as a screening technique. Accompanying studies regarding the hydrolytic stability of these fluorides in various buffer systems, as well as conditions of their long-term storage, were carried out. A simple procedure for the preparation of β-D-mannopyranosyl fluoride in gram quantities is given. Copyright (C) 2000 Elsevier Science Ltd.

Peracetylated α-D-glucopyranosyl fluoride and Peracetylated α-maltosyl fluoride

The X-ray analyses of 2,3,4,6-tetra-O-acetyl-α-D-glucopyran-osyl fluoride, C14H19FO9, (I), and the corresponding maltose derivative 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosyl-(1→4)- 2,3,6-tri-O-acetyl-α-D-glucopyran-osyl fluoride, C26H 35FO17, (II), are reported. These add to the series of published α-glycosyl halide structures; those of the Peracetylated α-glucosyl chloride [James & Hall (1969). Acta Cryst. A25, S196] and bromide [Takai, Watanabe, Hayashi & Watanabe (1976). Bull. Fac. Eng. Hokkaido Univ. 79, 101-109] have been reported already. In our structures, which have been determined at 140 K, the glycopyranosyl ring appears in a regular 4C1 chair conformation with all the substituents, except for the anomeric fluoride (which adopts an axial orientation), in equatorial positions. The observed bond lengths are consistent with a strong anomeric effect, viz. the C1-O5 (carbohydrate numbering) bond lengths are 1.381 (2) and 1.381 (3) A in (I) and (II), respectively, both significantly shorter than the C5-O5 bond lengths, viz. 1.448 (2) A in (I) and 1.444 (3) A in (II).

Synthesis of Glycosyl Fluorides by Photochemical Fluorination with Sulfur(VI) Hexafluoride

This study describes a new convenient method for the photocatalytic generation of glycosyl fluorides using sulfur(VI) hexafluoride as an inexpensive and safe fluorinating agent and 4,4′-dimethoxybenzophenone as a readily available organic photocatalyst. This mild method was employed to generate 16 different glycosyl fluorides, including the substrates with acid and base labile functionalities, in yields of 43%-97%, and it was applied in continuous flow to accomplish fluorination on an 7.7 g scale and 93% yield.

A Substituent-Directed Strategy for the Selective Synthesis of L-Hexoses: An Expeditious Route to L-Idose

L-Hexoses are rare but biologically significant components of various important biomolecules. However, most are prohibitively expensive (if commercially available) which limits their study and biotechnological exploitation. New, efficient methods to access L-hexoses and their derivatives are thus of great interest. In a previous study, we showcased a stereoselective Bu3SnH-mediated transformation of a 5-C-bromo-D-glucuronide to an L-iduronide. We have now drawn inspiration from this result to derive a new methodology – one that can be harnessed to access other L-hexoses. DFT calculations demonstrate that a combination of a β-F at the anomeric position and a methoxycarbonyl substituent at C-6 is key to optimising the selectivity for the L-hexose product. Our investigations have also culminated in the development of the shortest known synthetic route to a derivative of L-idose from a commercially available starting material (45 % yield over 3 steps). Collectively, these results address the profound lack of understanding of how to synthesise L-hexoses in a stereoselective fashion.