86420-73-7

Upstream product

• 110-86-1 pyridine 
• 98-88-4 benzoyl chloride 
• 18031-56-6 methyl-[O⁴,O⁶-((R)-benzylidene)-O³-trifluoroacetyl-α-D-glucopyranoside] 
• 3162-96-7 4,6-O-benzylidene-1-O-methyl-α-D-glucopyranoside 
• 1125-88-8 benzaldehyde dimethyl acetal 
• 1202384-89-1 C₂₃H₂₄O₉ 
• 100-52-7 benzaldehyde 
• 64552-06-3 methyl 4,6-O-benzylidene-α-D-galactopyranoside 
• 97-30-3 methyl-alpha-D-glucopyranoside 
• 71117-41-4 methyl 4,6-O-benzylidene-α-D-altropyranoside 
• 613-90-1 benzoyl cyanide 
• 71117-36-7 methyl 4,6-O-(S)-benzylidene-β-D-galactopyranoside 
• 93-97-0 benzoic acid anhydride 
• 71454-34-7 methyl O³-benzoyl-β-D-galactoside 

Downstream Products

• 75996-21-3 methyl-[O²-acetyl-O³-benzoyl-O⁴,O⁶-((R)-benzylidene)-α-D-glucopyranoside] 
• 120200-47-7 methyl-[O³-benzoyl-O⁴,O⁶-((R)-benzylidene)-O²-(toluene-4-sulfonyl)-α-D-glucopyranoside] 
• 389-05-9 methyl-[O³-benzoyl-O⁴,O⁶-((R)-benzylidene)-O²-trifluoroacetyl-α-D-glucopyranoside] 
• 144290-78-8 methyl-[O³-benzoyl-O⁴,O⁶-((R)-benzylidene)-O²-methyl-α-D-glucopyranoside] 
• 109010-32-4 Methyl-3-O-benzoyl-4,6-O-benzyliden-α-D-arabino-hexopyranosid-2-ulose 
• 94968-55-5 Methyl-3,4-di-O-benzoyl-α-D-glucopyranosid 
• 80245-05-2 methyl 3,6-di-O-benzoyl-α-D-glucopyranoside 
• 15038-71-8 methyl 2-O-benzyl-(R)-4,6-O-benzylidene-α-D-mannopyranoside 
• 32469-89-9 Methyl-3-O-benzoyl-4,6-O-benzyliden-2-desoxy-α-D-arabino-hexopyranosid 
• 108947-21-3 Methyl-3-O-benzoyl-4,6-O-benzyliden-3-C-2-methyl-α-D-arabino-hexopyranosid-2-ulose 
• 3150-15-0 methyl 2,3-anhydro-4,6-O-benzilidene-α-D-mannopyranoside 
• 110715-29-2 methyl 4,6-O-benzylidene-2-O-methyl-α-D-glucopyranoside 
• 1313374-89-8 methyl 2-O-acetyl-3-O-allyl-4,6-O-benzylidene-β-D-galactopyranosyl-(1->2)-3-O-benzoyl-4,6-O-benzylidene-α-D-glucopyranoside 
• 1313374-88-7 methyl 2-O-acetyl-3-O-allyl-4,6-O-benzylidene-α-D-galactopyranosyl-(1->2)-3-O-benzoyl-4,6-O-benzylidene-α-D-glucopyranoside 

Relevant academic research and scientific papers

SnCl2-Catalyzed Acetalation/Selective Benzoylation Sequence for the Synthesis of Orthogonally Protected Glycosyl Acceptors

Based on SnCl2-catalyzed acetalation and selective benzoylation, a one-pot strategy to efficiently synthesize orthogonally protected glycosyl acceptors with 2-OH/3-OH was developed. Consequently, 2-OBz or 3-OBz 4,6-O-benzylidene galactosides and glucosides were efficiently prepared in moderate to high yields starting from free galactosides and glucosides, and were used as valuable glycosyl acceptors for the synthesis of blood group antigens O and B analogues in this study.

Stannous chloride as a low toxicity and extremely cheap catalyst for regio-/site-selective acylation with unusually broad substrate scope

This work reports stannous chloride (SnCl2)-catalyzed regio-/site-selective acylation with unusually broad substrate scope. In addition to 1,2- and 1,3-diols and glycosides containing cis-vicinal diol, the substrate scope also includes glycosides without cis-vicinal diol. For such a substrate scope, usually, only methods using stoichiometric amounts of organotin reagents can lead to the same protection pattern with high selectivities and highly isolated yields (84-97% in most cases). Therefore, SnCl2, as a low toxicity and extremely cheap reagent, should be the best catalyst for regio-/site-selective acylation compared with any previously reported reagents. This journal is

A Potent Mimetic of the Siglec-8 Ligand 6’-Sulfo-Sialyl Lewisx

Siglecs are members of the immunoglobulin gene family containing sialic acid binding N-terminal domains. Among them, Siglec-8 is expressed on various cell types of the immune system such as eosinophils, mast cells and weakly on basophils. Cross-linking of Siglec-8 with monoclonal antibodies triggers apoptosis in eosinophils and inhibits degranulation of mast cells, making Siglec-8 a promising target for the treatment of eosinophil- and mast cell-associated diseases such as asthma. The tetrasaccharide 6’-sulfo-sialyl Lewisx has been identified as a specific Siglec-8 ligand in glycan array screening. Here, we describe an extended study enlightening the pharmacophores of 6’-sulfo-sialyl Lewisx and the successful development of a high-affinity mimetic. Retaining the neuraminic acid core, the introduction of a carbocyclic mimetic of the Gal moiety and a sulfonamide substituent in the 9-position gave a 20-fold improved binding affinity. Finally, the residence time, which usually is the Achilles tendon of carbohydrate/lectin interactions, could be improved.

DBN-Catalyzed Regioselective Acylation of Carbohydrates and Diols in Ethyl Acetate

The 1,5-diazabicyclo[4.3.0]non-5-ene (DBN)-catalyzed regioselective acylation of carbohydrates and diols in ethyl acetate has been developed. The hydroxyl groups can be selectively acylated by the corresponding anhydride in EtOAc in the presence of a catalytic amount (as low as 0.1 equiv.) of DBN at room temperature to 40 °C. This method avoids metal catalysts and toxic solvents, which makes it comparatively green and mild, and it uses less organic base compared with other selective acylation methods. Mechanism studies indicated that DBN could catalyze the selective acylation of hydroxyl moieties through a dual H-bonding interaction.

Diisopropylethylamine-triggered, highly efficient, self-catalyzed regioselective acylation of carbohydrates and diols

A diisopropylethylamine (DIPEA)-triggered, self-catalyzed, regioselective acylation of carbohydrates and diols is presented. The hydroxyl groups can be acylated by the corresponding anhydride in MeCN in the presence of a catalytic amount of DIPEA. This method is comparatively green and mild as it uses less organic base compared with other selective acylation methods. Mechanistic studies indicate that DIPEA reacts with the anhydride to form a carboxylate ion, and then the carboxylate ion could catalyze the selective acylation through a dual H-bonding interaction.

Highly Regioselective Monoacylation of Unprotected Glucopyranoside Using Transient Directing-Protecting Groups

The regioselective functionalization of monosaccharides is notoriously achieved using metal catalysis, lengthy synthetic strategies requiring protection/deprotection, various enzymes, or other methods that target cis-diols (and thus cannot be used with glucopyranose derivatives), In this paper, we report a new method using selected boronic acids as temporary protecting groups, and describe its application to the regioselective functionalization of methyl α-d-glucopyranoside, the most difficult monosaccharide to functionalize regioselectively. Generally, reactions of glucopyranosides may lead to a plethora of mono- and polyfunctionalized derivatives, yet our method gave the 3-O-acetylated, 2-O-benzoylated, and 2-O-pivaloylated derivatives of methyl α-d-glucopyranoside as major products. We focused on the use of recyclable and green temporary protecting groups (in a one-pot reaction) and on the modulation of the intramolecular hydrogen-bonding network using selected arylboronic acids. A complete scalable procedure leading to a single regioisomer from unprotected methyl α-d-glucopyranoside is presented.

Highly Efficient Selective Benzylation of Carbohydrates Catalyzed by Iron(III) with Silver Oxide and Bromide Anion as Co-catalysts

A highly efficient, green, and regioselective method for the benzylation of diols and polyols was developed. With the use of Ag2O (0.6 equiv.) and tetrabutylammonium bromide (0.1 equiv.) as co-catalysts, the iron(III)-catalyzed benzylation reaction proceeded to completion at 40 °C within 2–3 h and gave the products in high yields with high regioselectivities. A mechanism involving the principle of enhanced basicity of Ag2O by soft anions was proposed.

Enhanced site-selectivity in acylation reactions with substrate-optimized catalysts on solid supports

A concept for site selective acylation of poly-hydroxylated substrates is presented where polymer-supported catalysts are employed: catalytically active DMAP units were combined with a library of small molecule peptides attached to the solid phase with the goal to identify substrate-optimized catalysts through library screening. For selected examples, we demonstrate how the optimized catalysts can convert “their” substrate with a markedly enhanced site-selectivity, compared to only DMAP. Due to the solid support, product purification is significantly simplified, and the peptidic catalysts can be easily reused in multiple cycles while conserving its efficiency.

A green and convenient method for regioselective mono and multiple benzoylation of diols and polyols

An efficient method for regioselective benzoylation of diols and polyols was developed. The benzoylation is catalyzed by only 0.2 equiv of benzoate anion in acetonitrile with the addition of a stoichiometric amount of benzoic anhydride under very mild condition, leading to high yields. Compared with all other methods, this method shows particular advantage in regioselective multiple benzoylation of polyols, and in avoiding the use of any metal-based catalysts and any amine bases, which is more environment-friendly.

Investigation of benzoyloximes as benzoylating reagents: Benzoyl-Oxyma as a selective benzoylating reagent

Hydroxybenzotriazole (HOBt) and HOBt-derived reagents have been classified as Class I explosives, with restrictions on their transportation and storage. We explored a range of benzoylated oxime-based reagents as alternatives to benzoyloxybenzotriazole (BBTZ) for the selective benzoylation of carbohydrate polyols. Benzoylated oximes derived from 2-hydroximino-malononitrile, ethyl 2-hydroximino-2-cyanoacetate (Oxyma), and tert-butyl 2-hydroximino-2-cyanoacetate were most effective for benzoylation of a simple primary alcohol, with yields approaching that obtained for BBTZ. When applied to carbohydrate diols, the most effective reagent was identified as benzoyl-Oxyma. Benzoyl-Oxyma is a highly crystalline, readily prepared alternative to BBTZ, useful in the selective benzoylation of carbohydrate polyols.