biostudies-literaturePlangger ICenter for Molecular Biosciences, University of InnsbruckAustrian Science Fund FWFEuropean Research Council7151-7156https://www.ebi.ac.uk/biostudies/studies/S-EPMC7613685biostudies-literatureUnknown24(39)We present the first total synthesis of eight <i>ent</i>-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 <i>ent</i>-pimaranes bearing different modifications in the A- and C-rings.Organic lettersShort, Divergent, and Enantioselective Total Synthesis of Bioactive <i>ent</i>-Pimaranes.PMC7613685P 31023101000060Plangger IWurst KMagauer TfalseShort, Divergent, and Enantioselective Total Synthesis of Bioactive <i>ent</i>-Pimaranes.We present the first total synthesis of eight <i>ent</i>-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 <i>ent</i>-pimaranes bearing different modifications in the A- and C-rings.2022-01-01T00:00:00Z2022 Oct2025-04-04T02:26:05.556Z2025-04-04T02:26:05.556ZS-EPMC76136853617046610.1021/acs.orglett.2c02843