Carbene-Mediated Quaternarization of the Anomeric Position of Carbohydrates: Synthesis of Allylic Ketopyranosides, Access to the Missing α-Gluco and β-Manno Stereoisomers, and Preparation of Quaternary 2-Deoxy 2-Acetamido Sugars

Kevin Mebarki , Marine Gavel (1) , Floriane Heis , Antoine Yvan , Philippe Joosten , Thomas Lecourt (1) , Kévin Mébarki , Antoine Joosten (1)

1 COBRA - Chimie Organique et Bioorganique : Réactivité et Analyse

Following our work on the C–H functionalization of carbohydrates by the 1,5 insertion of metal–carbenes, we report herein the robust and scalable conversion of sugar γ-lactones into highly valuable glycosides having a quaternary anomeric position substituted by an allyl chain ready for further functionalization. A divergent synthetic approach furthermore provided a straightforward access to ketopyranosides with a large chemo- and stereodiversity at position 2.

Domains: Chemical Sciences

Kevin Mebarki, Marine Gavel, Floriane Heis, Antoine Yvan, Philippe Joosten, et al.. Carbene-Mediated Quaternarization of the Anomeric Position of Carbohydrates: Synthesis of Allylic Ketopyranosides, Access to the Missing α-Gluco and β-Manno Stereoisomers, and Preparation of Quaternary 2-Deoxy 2-Acetamido Sugars. Journal of Organic Chemistry, 2017, 82 (17), pp.9030-9037. ⟨10.1021/acs.joc.7b01493⟩. ⟨hal-02354798⟩