Short, Divergent, and Enantioselective Total Synthesis of Bioactive ent-Pimaranes

[Image: see text] We present the first total synthesis of eight ent-pimaranes via a short and enantioselective route (11–16 steps). Key features of the divergent synthesis are a Sharpless asymmetric dihydroxylation, a Brønsted acid catalyzed cationic bicyclization, and a mild Rh-catalyzed arene hydrogenation for rapid access to a late synthetic branching point. From there on, selective functional group manipulations enable the synthesis of ent-pimaranes bearing different modifications in the A- and C-rings.