The first total synthesis of muricadienin, the unsaturated putative precursor in the biosynthesis of trans- and cis-solamin is described. Key steps in the synthesis are a chemoselective hydroboration, a Z-selective Wittig reaction, and a Fries rearrangement for introducing the terminal α-substituted butenolide. Thus, muricadienin can be synthesized in 11 steps from commercially available starting materials in 42% overall yield.