Efficient Synthesis of the Deoxysugar Part of Versipelostatin by Direct and Stereoselective Glycosylation and Revision of the Structure of the Trisaccharide Unit

Sweets for my sweet ! Efficient synthesis of the deoxysugar part of versipelostatin (VST) was achieved by direct and stereoselective glycosidation of the reduced VST aglycon. Comparison of the synthetic and natural VST products using NMR indicate that VST has a β‐d‐digitoxose‐(1,4)‐α‐l‐oleandrose‐(1,4)‐β‐d‐digitoxose trisaccharide. A biological assay indicates that the deoxyoligosaccharide unit of the synthetic glycoside is important for biological activity.