Enantioselective Total Synthesis of (+)-Gephyrotoxin 287C

A synthesis of (+)-gephyrotoxin 287C using (<i>S</i>)-phenylglycinol-derived tricyclic lactam <b>7</b> as the starting enantiomeric scaffold is reported. From the stereochemical standpoint, the key steps are the generation of the DHQ C-5 stereocenter by hydrogenation of the C–C double bond, removal of the chiral inductor to give a <i>cis</i>-DHQ, introduction of the DHQ C-2 substituent, completion of the (<i>Z</i>)-enyne moiety, and generation of the C-1 stereocenter during closure of the pyrrolidine ring