A convergent total synthesis of ouabagenin† †Electronic supplementary information (ESI) available: Characterization data for all new compounds, experimental procedures. CCDC 1027184 and 1027185. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc00212e Click here for additional data file. Click here for additional data file.

A convergent total synthesis of ouabagenin, an aglycon of cardenolide glycoside ouabain, was achieved by assembly of the AB-ring, D-ring and butenolide moieties. The multiply oxygenated cis-decalin structure of the AB-ring was constructed from (R)-perillaldehyde through the Diels–Alder reaction and sequential oxidations. The intermolecular acetal formation of the AB-ring and D-ring fragments, and combination of the intramolecular radical and aldol reactions, assembled the requisite steroidal skeleton in a stereoselective fashion. Finally, stereoselective installation of the C17-butenolide via the Stille coupling and hydrogenation led to ouabagenin.