Fissions of 14α, 15α-epoxy ring in a cardenolide with perchloric acid and with hydrogen chloride were found to afford 14β-steroids. With the use of these reactions, some D-ring-transformed compounds of digitoxigenin, e.g. 15α-hydroxydigitoxigenin, and 14-chloro-3β, 15α-dihydroxy- and-3β-hydroxy-14β, 15β-epoxy-cardenolides, were synthesized.
