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Reagent Controlled Stereoselective Assembly of α-(1,3)-Glucans
Liming Wang1, Herman S Overkleeft1, Gijsbert A van der Marel1
1Leiden Institute of Chemistry Leiden University Einsteinweg 55 2333 CC Leiden The Netherlands.
Abstract:
Pre-activation based glycosylations have become a very powerful tool in the assembly of oligosaccharides and the use of nucleophilic additives allows for the in situ generation of reactive intermediates with tailored reactivity. We here use a glycosylation strategy that is based on the use of per-benzylated imidate building blocks for the fully stereoselective construction of a spacer equipped Aspergillus fumigatus α-1,3-octaglucan. We have used the trimethylsilyl iodide (TMSI)-triphenylphosphine oxide (Ph3P=O) for the stereoselective installation of an azidopropanol spacer and triflic acid (TfOH)-dimethyl formamide (DMF) enabled glycosylations for the coupling reactions with the secondary glucosyl C-3-alcohols. An operationally simple in situ activation coupling procedure is introduced and used for the final glycosylation events towards the octasaccharide.
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