Fluorine‐Directed β‐Galactosylation: Chemical Glycosylation Development by Molecular Editing

Abstract

Validation of the 2-fluoro substituent as an inert steering group to control chemical glycosylation is presented. A molecular editing study has revealed that the exceptional levels of diastereocontrol in glycosylation processes by using 2-fluoro-3,4,6-tri-O-benzyl glucopyranosyl trichloroacetimidate (TCA) scaffolds are a consequence of the 2R,3S,4S stereotriad. This study has also revealed that epimerization at C4, results in a substantial enhancement in β-selectivity (up to β/α 300:1).

Highly Efficient Singlet Oxygen Generators Based on Ruthenium Phthalocyanines: Synthesis, Characterization and in vitro Evaluation for Photodynamic Therapy

“…In order to verify the configuration of the Glc moiety in L4 , we proceeded with its acetylation in the presence of DMAP and pyridine (Scheme ), as described in the literature . The acetylated ligands were analyzed by 1 H NMR spectroscopy.…”

Analysis of carbohydrates and glycoconjugates by matrix‐assisted laser desorption/ionization mass spectrometry: An update for 2011–2012

“…Use of anomeric sulfonium ions as glycosyl donors (Fang et al, 2012) Oligosaccharides MALDI Fluorine-directed -galactosylation (Durantie et al, 2012) Oligosaccharides TOF (DHB) Acceptor-influenced and donor-tuned basepromoted glycosylation (Boettcher et al, 2012) Oligosaccharides TOF (DHB)…”

Introducing affinity and selectivity into galectin-targeting nanoparticles with fluorinated glycan ligands

“…24 Fluorination of glycans inuences their physicochemical properties and hence modulates their biological function. [25][26][27][28] While uorine substitution has little effect on glycan conformation, 29,30 it can inuence hydrogen bonding properties of adjacent hydroxyl groups, 31,32 and uorine itself is a weak hydrogen bond acceptor but not a hydrogen bond donor. 33,34 Furthermore, uorine atoms can form attractive multipolar interactions with proteins, 35,36 and these have been observed with uorinated carbohydrate derivatives, 37 including galectin binders.…”