Versatile acetylation of carbohydrate substrates with bench-top sulfonic acids and application to one-pot syntheses of peracetylated thioglycosides

Chao, Chin Sheng; Chen, Min Chun; Lin, Shih Che; Mong, Kwok-Kong Tony

doi:10.1016/j.carres.2008.01.014

Cited by 39 publications

(25 citation statements)

References 39 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Synthesis and affinity of the minimal binding epitope. Sialidation of the galactose acceptor 4 [41] with sialic acid donor 3 [42] yielded disaccharide 5. The highest yield and the best αselectivity were obtained using NIS/TfOH as promoter, and MeCN/DCM as solvent.…”

Section: Resultsmentioning

confidence: 99%

“…5-acetamido-4,7,8,9-tetra-O-acetyl-3,5-dideoxy-dglycero-α-d-galacto-2-nonulopyranosylonate)-(2!3)-6-O-tert-butyldiphenylsilyl-β-d-galactopyranoside (5). To a suspension of 3 [42] (3.65 g, 6.10 mmol), 4 [41] (1.20 g, 2.77 mmol) and 3 Å molecular sieves in MeCN/DCM (5 : 3, 70 mL) at À 40°C, was added Niodosuccinimide (2.74 g, 12.1 mmol), followed by dropwise addition of TfOH (98 μL, 1.1 mmol). The reaction mixture was stirred at À 40°C for 16 h under argon and then was neutralized with NEt 3 .…”

Section: Methodsmentioning

confidence: 99%

“…. To a solution of 3 [42] (2.00 g, (methyl 5-acetamido-9-azido-2,3,5,9-tetradeoxy-2-thio-dglycero-β-d-galacto-2-nonulopyranosylonate) (42). To a solution of 41 (570 mg, 0.98 mmol) in dry DMF (15 mL) were added NaN (313 mg, 4.82 mmol) and 15-crown-5 (0.1 mL, 0.49 mmol).…”

Section: P-tolyl (Methyl 5-acetamido-235-trideoxy-2-thio-d-glycero-mentioning

confidence: 99%

See 2 more Smart Citations

A Potent Mimetic of the Siglec‐8 Ligand 6’‐Sulfo‐Sialyl Lewis^x

et al. 2020

View full text Add to dashboard Cite

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.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

A Potent Mimetic of the Siglec‐8 Ligand 6’‐Sulfo‐Sialyl Lewis^x

et al. 2020

View full text Add to dashboard Cite

show abstract

“…Sulfuric acid is commonly used in the synthesis of sugar acetates 19 and in the catalysis of the anomerisation of glucose pentacetates into α-anomer. 20 Selective acetylation of the hydroxyl group of glucosamine 1 was achieved by sulfuric acid catalysis, which blocks the amino group by salt formation.…”

Section: Resultsmentioning

confidence: 99%

A Facile and Stereoselective Synthesis of 3,4,6-Tri-O-Acetyl-2-Deoxy-2-Phthalimido-β-D-Glucopyranosyl Chloride

Cao

Liu

et al. 2013

Journal of Chemical Research

View full text Add to dashboard Cite

Acetylation of D-glucosamine catalysed by sulfuric acid and N-phthaloylation of the glucosyl acetate yielded 1,3,4,6tetra-O-acetyl-2-deoxy-2-phthalimido-α-D-glucopyranose. This gave the corresponding pure β-glucosyl chloride upon treatment with PCl 5 -BF 3 . An anomeric chlorination with thionyl chloride combined with the Lewis acids (ZnCl 2 , SnCl 4 and BiCl 3 ) resulted in an α/β anomer mixture.

show abstract

“…27 Moreover, Mong and co-workers investigated the acid-catalyzed peracetylation of 2 using p -toluene sulfonic acid and excess Ac 2 O at 45 ° C yielding 3 (80%) and 5% of 9 . 34 Microwave-assisted heating in the presence of an acid catalyst, therefore, may offer a simple and expedient solution phase β-elimination protocol. To test our hypothesis that SSA can catalyze the β-elimination at C-2, we investigated the direct synthesis of 9 from 2 using our previous microwave-assisted peracetylation conditions as starting point.…”

mentioning

confidence: 99%

One-pot SSA-catalyzed β-elimination: an efficient and inexpensive protocol for easy access to the glycal of sialic acid

Paragas

Monreal

Vasil

et al. 2015

Carbohydrate Research

View full text Add to dashboard Cite

Neu5Ac2en1Me per-OAc, the fully protected glycal of sialic acid, is a key intermediate in the discovery of therapeutics and diagnostics, including anti-influenza drugs and proteolysis resistant peptidomimetic foldamers. The synthesis of this sialic acid derivative, however, still relies on standard sugar chemistry that utilizes multi-step methodologies. Herein we report a facile and highly efficient microwave-assisted preparation of Neu5Ac1Me using silica sulfuric acid (SSA) as solid-supported acid catalyst that is one- to two-orders of magnitude faster than standard procedures. We also describe the microwave-assisted and SSA-catalyzed one-pot, rapid, solvent free reaction that combines both peracetylation and β-elimination reactions in one step to generate the glycal from Neu5Ac1Me. We coined the term One-pot SSA-catalyzed Technology for β-Elimination Protocol (OneSTEP) to describe this least laborious, most efficient, and practical preparation to date of Neu5Ac2en1Me per-OAc in terms of yield, time, reagent cost, and waste generation.

show abstract

Versatile acetylation of carbohydrate substrates with bench-top sulfonic acids and application to one-pot syntheses of peracetylated thioglycosides

Cited by 39 publications

References 39 publications

A Potent Mimetic of the Siglec‐8 Ligand 6’‐Sulfo‐Sialyl Lewis^x

A Potent Mimetic of the Siglec‐8 Ligand 6’‐Sulfo‐Sialyl Lewis^x

A Facile and Stereoselective Synthesis of 3,4,6-Tri-O-Acetyl-2-Deoxy-2-Phthalimido-β-D-Glucopyranosyl Chloride

One-pot SSA-catalyzed β-elimination: an efficient and inexpensive protocol for easy access to the glycal of sialic acid

Contact Info

Product

Resources

About

Versatile acetylation of carbohydrate substrates with bench-top sulfonic acids and application to one-pot syntheses of peracetylated thioglycosides

Cited by 39 publications

References 39 publications

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

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

A Facile and Stereoselective Synthesis of 3,4,6-Tri-O-Acetyl-2-Deoxy-2-Phthalimido-β-D-Glucopyranosyl Chloride

One-pot SSA-catalyzed β-elimination: an efficient and inexpensive protocol for easy access to the glycal of sialic acid

Contact Info

Product

Resources

About

A Potent Mimetic of the Siglec‐8 Ligand 6’‐Sulfo‐Sialyl Lewis^x

A Potent Mimetic of the Siglec‐8 Ligand 6’‐Sulfo‐Sialyl Lewis^x