Preparation of aminoethyl glycosides for glycoconjugation

Abstract

SummaryThe synthesis of a number of aminoethyl glycosides of cell-surface carbohydrates, which are important intermediates for glycoarray synthesis, is described. A set of protocols was developed which provide these intermediates, in a short number of steps, from commercially available starting materials.

The Amadori Rearrangement for Carbohydrate Conjugation: Scope and Limitations

“…To this end, 3‐ O ‐(aminopropyl)‐functionalized mannosides 20 and 23 were synthesized by applying a procedure for tin‐mediated regioselective etherification of glycosides, which we have disclosed earlier (Scheme 4). 16 Thus, mannosides 18 17 and 21 ,18 respectively, were treated with dibutyltin oxide to achieve the corresponding stannylidene acetal intermediates. These were treated with N ‐(3‐bromopropyl)phthalimide in the same reaction vessel after the solvent was exchanged from MeOH to N , N ‐dimethylformamide (DMF) to deliver the respective 3‐ O ‐functionalized mannosides 19 and 22 after regioselective opening of the tin acetal ring.…”

“…2‐(Benzyloxycarbonylamino)ethyl 3‐ O ‐(3‐Phthalimidopropyl)‐α‐ d ‐mannopyranoside (19): To a solution of the benzyloxycarbonyl‐protected mannoside 18 17 (3.29 g, 9.19 mmol) in anhydrous methanol (90 mL), dibutyltin oxide (2.40 g, 9.65 mmol) was added, and the solution was heated to reflux for 2 h. The solvent was evaporated, and the crude product was disolved in anhydrous N , N ‐dimethylformamide (90 mL). N ‐(3‐Bromopropyl)phthalimide (9.12 g, 34.0 mmol) and cesium fluoride (1.40 g, 9.19 mmol) were added, and the reaction mixture was stirred at room temperature for 3 d. The solvent was then evaporated, and purification of the crude product by column chromatography (CH 2 Cl 2 /EtOAc/MeOH, 10:5:1 → 5:5:1) gave 19 (1.87 g, 3.44 mmol, 37 %) as colorless foam.…”

Glycosylation Characterization of Human and Porcine Fibrinogen Proteins by Lectin-Binding Biophotonic Microarray Imaging

“…The monosaccharide standards Glc, GlcNAc, Gal and Man aminoethyl glycosides were prepared as published elsewhere 28 . The aminoethyl glycosides were coupled to the carboxyl groups in SAMs allowing the surface sugar concentration to be varied by varying the linker-spacer ratio.…”

“…The gold nanoparticle array spots can be functionalised by self-assembling monolayers (SAMs) which carry a terminal carboxylic group (linker) for chemical modification and a terminal hydroxyl group (spacer), respectively [26][27] . The carboxylic group can be used to couple various different chemically modified sugars on the surface 28 . The hydroxyl group carrying molecule spacer allow spacer dilutions, which is important to understand the different affinities of lectins to high and low concentrated sugars on the surface [29][30] .…”

Design and syntheses of mono and multivalent mannosyl-lipoconjugates for targeted liposomal drug delivery

“…A daily supply of water was obtained from Millipore Simplicity-Personal ultra-pure water system (Bedford, MA, USA). 2-aminoethyl-α-D-mannopyranoside 1 and (R)-(2,3,4,6-tetra-O-benzyl-α-D-mannopyranosyloxy)-2-metylpropionic acid 2 were prepared according to the literature procedures (Ribić et al, 2009;Šardzik et al, 2010).…”