Lewis acid-catalysed nucleophilic opening of a bicyclic hemiaminal followed by ring contraction: Access to functionalized L-idonojirimycin derivatives.


Equipe Synthèse Organique - Groupe Glycochimie Institut de Chimie des Milieux et Materiaux de Poitiers (IC2MP), UMR-CNRS 7285, Université de Poitiers, Bâtiment B28, TSA 51106, 4 rue Michel Brunet, 86073, Poitiers cedex 9, France. Electronic address: [Email]


The Lewis acid-catalyzed nucleophilic opening of a D-gluco-configured bicyclic hemiaminal has been examined. Several Lewis acids and silylated nucleophiles have been screened allowing the introduction of acetophenone, phosphonate or nitrile at the pseudoanomeric position in satisfactory yields and high 1,2 trans stereoselectivities. Their skeletal rearrangement triggered by the N-benzyl anchimeric assistance provided the corresponding L-ido-configured piperidines displaying various functional groups at C-6 position in good yield.


Bicycle opening,Hemiaminal,Iminosugar,Skeletal rearrangement,