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

Nicolas Auberger (1) , Benjamin Onfroy (1) , Nathalie Fontelle (1) , Quentin Foucart (1) , Yves Bleriot (1)

1 OrgaSynth - Synthèse organique [E5 – IC2MP équipe 5]

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-idoconfigured piperidines displaying various functional groups at C-6 position in good yield.

Mots clés: Bicycle opening; Iminosugar; Hemiaminal; Skeletal rearrangement

Domaines: Chimie organique; Chimie thérapeutique

Nicolas Auberger, Benjamin Onfroy, Nathalie Fontelle, Quentin Foucart, Yves Bleriot. Lewis acid-catalysed nucleophilic opening of a bicyclic hemiaminal followed by ring contraction: Access to functionalized L-idonojirimycin derivatives. Carbohydrate Research, 2019, 472, pp.65-71. ⟨10.1016/j.carres.2018.11.008⟩. ⟨hal-02180492⟩