Synthesis of\nAcovenosides: Cardiac Glycosides with\nPotent Antitumor Activities

Acovenoside\nA (<b>1</b>), a cardiac glycoside featuring a\nunique l-acovenose at C-3 and a 1β,3β,14β-trihydroxy\naglycone (namely, acovenosigenin A), shows promising antiproliferative\nactivities. Herein, we report the synthesis of acovenoside A (<b>1</b>) together with a panel of its congeners. The synthesis features\nthe stereoselective introduction of the 1β,14β-OH and\nC17-butenolide moieties starting from androstenedione (<b>7</b>) and gold(I)-catalyzed glycosylation with superarmed glycosyl <i>ortho</i>-alkynylbenzoates as donors.