Stereoselective Synthesis of Iminosugar 2-Deoxy(thio)glycosides from Bicyclic Iminoglycal Carbamates Promoted by Cerium(IV) Ammonium Nitrate and Cooperative Brønsted Acid-Type Organocatalysis
Irene Herrera‐González, Elena M. Sánchez‐Fernández, Abhijit Sau, Cristina Nativi, José M. Garcı́a Fernández, M. Carmen Galán, Carmen Ortiz Mellet
Abstract
The first examples of iminosugar-type 2-deoxy(thio)glycoside mimetics are reported. The key step is the activation of a bicyclic iminoglycal carbamate to generate a highly reactive acyliminium cation. Cerium(IV) ammonium nitrate efficiently promoted the formation of 2-deoxy S-glycosides in the presence of thiols, probably by in situ generation of catalytic HNO3, with complete α-stereoselectivity. Cooperative phosphoric acid/Schreiner’s thiourea organocatalysis proved better suited for generating 2-deoxy O-glycosides, significantly broadening the scope of the approach.
Topics & Concepts
ChemistryThio-IminosugarOrganocatalysisStereoselectivityBicyclic moleculeCeriumGlycosideOrganic chemistryCombinatorial chemistryCatalysisStereochemistryMedicinal chemistryEnantioselective synthesisEnzymeCarbohydrate Chemistry and SynthesisGlycosylation and Glycoproteins ResearchChemical Synthesis and Analysis