Polyhalogenated Carbohydrates: Synthesis and Applications of Sugar Halides from Fluorine to Iodine DOI Creative Commons
Olivier Lessard,

Danny Lainé,

Denis Giguère

et al.

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(16)

Published: March 5, 2024

Abstract Polyfluorinated carbohydrates have attracted attention in the last decades. This is due to interesting properties of such organofluorines. What about other halogens? Since discovery sucralose (a trichlorinated disaccharide) more than 50 years ago, only a handful chlorinated, brominated, or iodinated been reported. review focuses on synthesis polyhalogenated carbohydrates, including sugar inter‐halides, but excluding polyfluorinated sugars. An overview current state art their potential application also described.

Language: Английский

The Synthesis and Glycoside Formation of Polyfluorinated Carbohydrates DOI Creative Commons
Kler Huonnic, Bruno Linclau

Chemical Reviews, Journal Year: 2022, Volume and Issue: 122(20), P. 15503 - 15602

Published: May 25, 2022

Fluorinated carbohydrates have found many applications in the glycosciences. Typically, these contain fluorination at a single position. There are not involving polyfluorinated carbohydrates, here defined as monosaccharides which more than one carbon has least fluorine substituent directly attached to it, with notable exception of their use mechanism-based inhibitors. The increasing attention carbohydrate physical properties, especially around lipophilicity, resulted surge interest for this class compounds. This review covers considerable body work toward synthesis hexoses, pentoses, ketosugars, and aminosugars including sialic acids nucleosides. An overview current state art glycosidation is also provided.

Language: Английский

Citations

26
Automated Glycan Assembly of 19F‐labeled Glycan Probes Enables High‐Throughput NMR Studies of Protein–Glycan Interactions DOI
Giulio Fittolani, Elena Shanina, Mónica Guberman

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(24), P. 13302 - 13309

Published: March 30, 2021

Protein-glycan interactions mediate important biological processes, including pathogen host invasion and cellular communication. Herein, we showcase an expedite approach that integrates automated glycan assembly (AGA) of

Language: Английский

Citations

28
Neighboring Group Participation of Benzoyl Protecting Groups in C3‐ and C6‐Fluorinated Glucose DOI
Kim Greis, Carla Kirschbaum, Giulio Fittolani

et al.

European Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 2022(15)

Published: March 25, 2022

Fluorination is a potent method to modulate chemical properties of glycans. Here, we study how C3- and C6-fluorination glucosyl building blocks influence the structure intermediate glycosylation reaction, glycosyl cation. Using combination gas-phase infrared spectroscopy first-principles theory, cations generated from fluorinated non-fluorinated monosaccharides are structurally characterized. The results indicate that neighboring group participation C2-benzoyl protecting dominant structural motif for all blocks, correlating with β-selectivity observed in reactions. signatures benzoyl enhanced by resonance effects. Participation remote acyl groups such as Fmoc or benzyl on other hand unfavored. introduction less bulky fluorine leads change conformation ring pucker, whereas active dioxolenium site remains unchanged.

Language: Английский

Citations

19
Drug Discovery Based on Fluorine-Containing Glycomimetics DOI Creative Commons

Xing-Xing Wei,

Pengyu Wang, Liu Fen

et al.

Molecules, Journal Year: 2023, Volume and Issue: 28(18), P. 6641 - 6641

Published: Sept. 15, 2023

Glycomimetics, which are synthetic molecules designed to mimic the structures and functions of natural carbohydrates, have been developed overcome limitations associated with carbohydrates. The fluorination carbohydrates has emerged as a promising solution dramatically enhance metabolic stability, bioavailability, protein-binding affinity In this review, methods used prepare fluorinated effects on physical, chemical, biological characteristics sugars, activities sugars presented.

Language: Английский

Citations

11
Quantifying Siglec-sialylated ligand interactions: a versatile 19F-T2 CPMG filtered competitive NMR displacement assay DOI Creative Commons
Unai Atxabal, Andrea Fernández,

María Jesús Moure

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(27), P. 10612 - 10624

Published: Jan. 1, 2024

Sialic-acid-binding immunoglobulin-like lectins (Siglecs) are integral cell surface proteins crucial for the regulation of immune responses and maintenance tolerance through interactions with sialic acids.

Language: Английский

Citations

4
Stereoselective strain-release Ferrier rearrangement: the dual role of catalysts DOI Creative Commons
Huajun Zhang, Aoxin Guo, Han Ding

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(16), P. 4470 - 4478

Published: Jan. 1, 2024

ACu(OTf) 2 /Fe(OTf) 3 -promoted facile and stereoselective synthesis of 2,3-unsaturated glycosides through Ferrier rearrangement rationally designed glycals with C3-CCBz. The dual roles the metal catalysts in reaction are explored DFT.

Language: Английский

Citations

4
Structural glycobiology – from enzymes to organelles DOI Creative Commons
Courtney J. Mycroft‐West, Miron Leanca, Liang Ping Wu

et al.

Biochemical Society Transactions, Journal Year: 2025, Volume and Issue: 53(1)

Published: Jan. 31, 2025

Biological carbohydrate polymers represent some of the most complex molecules in life, enabling their participation a huge range physiological functions. The complexity biological carbohydrates arises from an extensive enzymatic repertoire involved construction, deconstruction and modification. Over past decades, structural studies processing enzymes have driven major insights into mechanisms, supporting associated applications across medicine biotechnology. Despite these successes, our understanding how multienzyme networks function to create polysaccharides is still limited. Emerging techniques such as super-resolution microscopy cryo-electron tomography are now investigation native systems at near molecular resolutions. Here, we review classical vitro processing, alongside recent situ glycosylation-related processes. While considerable technical challenges remain, integration mechanisms with true context promises transform regulation, shining light upon processes driving functional essential biomolecules.

Language: Английский

Citations

0
Synthesis of Fluorinated Glycotope Mimetics Derived from Streptococcus pneumoniae Serotype 8 CPS DOI Open Access

Daniel Gast,

Sebastian Neidig,

Maximilian Reindl

et al.

International Journal of Molecular Sciences, Journal Year: 2025, Volume and Issue: 26(4), P. 1535 - 1535

Published: Feb. 12, 2025

Fluorination of carbohydrates is a promising strategy to produce glycomimetics with improved pharmacological properties, such as increased metabolic stability, bioavailability and protein-binding affinity. Fluoroglycans are not only interest inhibitors chemical probes but increasingly being used develop potential synthetic vaccine candidates for cancer, HIV bacterial infections. Despite their attractiveness, the synthesis fluorinated oligosaccharides still challenging, emphasizing need efficient protocols that allow site-specific incorporation fluorine atoms (especially at late stages synthesis). This particularly true development fully candidates, whose (modified) carbohydrate antigen structures (glycotopes) per se comprise multistep routes. Based on known minimal protective epitope from capsular polysaccharide S. pneumoniae serotype 8, panel six novel F-glycotope mimetics was synthesized, equipped amine linkers subsequent conjugation immunogens. Next stepwise assembly via building blocks, corresponding 6F-substituted derivatives could be obtained by microwave-assisted, nucleophilic late-stage fluorination tri- tetrasaccharidic precursors in high yields. The described allowed preparation targeted sufficient quantities future immunological studies.

Language: Английский

Citations

0
Concept of Future Glycoprotein Drugs: Synthesis of a Thioglycosidically Linked α-N-Acetylgalactosamine-Carrying Cyclic Peptide as a Model of Miniature Macrophage Activating Factor DOI

Kotaro Kanzaki,

Yuma Nakagomi,

Yuri Asami

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: March 13, 2025

Glycoproteins are often considered as drug candidates. However, the regulation of post-translational glycan attachment remains an issue. We hypothesized that replacing oxygen atom in glycosidic linkage with sulfur atoms would stabilize labile against glycosidases, resulting improved pharmacokinetics. In this study, we focused on macrophage-activating factor (MAF) carrying O-linked N-acetylgalactosamine (GalNAc) and creating a miniature glycopeptide associated MAF. A partial structure MAF chemical mutation at three amino acid residues was designed which threonine replaced cysteine (Cys), leading to thioglycosidically linked GalNAc conformationally stable cyclic peptide due disulfide bond. GalNAc-Cys used solid-phase synthesis, desired synthesized. synthesis GalNAc-Cys, glycosylation reactions were carried out based hard soft acids bases concept, where glycosyl trichloroacetimidate fluoride successfully couple thiol group Cys. also evaluated substrate α-GalNAc-ase shown resist hydrolysis, supporting our concept. The synthesized induced LPS-assisted IL-12 production resisted α-GalNAc-ase.

Language: Английский

Citations

0
Origami with small molecules: exploiting the C–F bond as a conformational tool DOI Creative Commons
Patrick Ryan, Ramsha Iftikhar, Luke Hunter

et al.

Beilstein Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 21, P. 680 - 716

Published: April 2, 2025

When present within an organic molecule, the C–F bond tends to align in predictable ways with neighbouring functional groups, due stereoelectronic effects such as hyperconjugation and electrostatic attraction/repulsion. These fluorine-derived conformational have been exploited control shapes, thereby enhance properties, of a wide variety molecules including pharmaceutical agents, liquid crystals, fragrance chemicals, organocatalysts, peptides. This comprehensive review summarises developments this field during period 2010–2024.

Language: Английский

Citations

0