A Short Route to the Synthesis of Digoxose Trisaccharide Glycal Donor via Mislow–Evans Rearrangement

Abstract

The Mislow–Evans rearrangement was used as a key reaction to construct digitoxose-derived glycals. The same rearrangement was iteratively performed on di- and trisaccharides to form the digoxose glycal donor component present in the cardenolides digitoxin, digoxin, and gitoxin. The scalability of the trisaccharide synthesis was shown by performing the reactions on a multigram scale. Glycosylation reactions were also performed between the synthesized digoxin glycal donor and aglycons digoxigenin and gitoxigenin to synthesize novel cardenolide derivatives.