The stereocontrolled total synthesis of (−)-myriocin 1 is reported. Optically active epoxide 9 was converted from symmetrical cyclohexadiene 8, utilizing an enzymatic kinetic resolution. The three sequential stereogenic centers of 1 were constructed by a regioselective epoxide- opening reaction and a Hofmann rearrangement. Elongation of the side chain was efficiently accomplished by the Julia–Kocienski reaction.
