Enantioselective Total Syntheses of (+)-Fendleridine and (+)-Acetylaspidoalbidine.

Enantioselective syntheses of hexacyclic aspidoalbidine alkaloids (+)-fendleridine (2) and (+)-acetylaspidoalbidine (3) are described. These syntheses feature an asymmetric decarboxylative allylation and photocyclization of a highly substituted enaminone. Also, the synthesis highlights the formation of a C19-hemiaminal ether via a reduction/condensation/intramolecular cyclization cascade with the C21-alcohol. The present synthesis provides convenient access to the aspidoalbidine hexacyclic alkaloid family in an efficient manner.