Stereoselective Access to Iminosugar C,C-Glycosides from 6-Azidoketopyranoses
Zakaria Debbah1, Jérôme Marrot2, Nicolas Auberger1
1Université de Poitiers, IC2MP, UMR CNRS 7285, Equipe "OrgaSynth", Groupe Glycochimie, 4 rue Michel Brunet, 86073 Poitiers Cedex 9, France.
Abstract:
We report the synthesis of iminosugar C,C-glycosides starting from 6-azidoketopyranoses. Their Staudinger-azaWittig-mediated cyclization provided bicyclic N,O-acetals, which were stereoselectively opened with AllMgBr to afford β-hydroxyazepanes with a quaternary carbon α to the nitrogen. Their ring contraction via a β-aminoalcohol rearrangement produced the six-membered l-iminosugars with two functional handles at the pseudoanomeric position. Inversion of the free OH at the azepane level furnished the d-iminosugars.
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