Application of Redox-Active Ester Catalysis to the Synthesis of Pyranose Alkyl <i>C</i>-Glycosides
Joseph R. Romeo, Jon D. Lucera, Drew Jensen, Luke M. Davis, Clay S. Bennett
Abstract
The direct coupling of shelf-stable, tetrachloro- N -hydroxyphthalimide ester (TCNHPI) glycosyl donors with a variety of alkylzinc reagents under redox catalysis is described. Alkyl C -glycosides are formed directly by a decarboxylative, Negishi-type process in 31–73% yields without the need for photocatalytic activation or additional reductants. Extension of this approach to the coupling of TCNHPI donors with stereodefined α-alkoxy furan-containing alkylzinc halides enabled de novo synthesis of methylene-linked exo-C -disaccharides via an Achmatowicz rearrangement.
Topics & Concepts
ChemistryAlkylReagentCatalysisPyranoseCombinatorial chemistryGlycosylRedoxNegishi couplingFuranMethyleneGlycosideOrganic chemistryCarbohydrate Chemistry and SynthesisSynthetic Organic Chemistry MethodsAsymmetric Synthesis and Catalysis