Abstract: A 21-step stereoselective total synthesis of (f)-K-76 is reported starting from 6- acetoxy-4-methyl-4-hexenal (23) and 3-methoxy-2-cyclohexenone (6). The key steps in the synthesis are the demonstration that alkylidenecyclopropanes such as 27 can serve as initiators for electrophile-induced polyene cyclizations, the development of a new method for conversion of organomercurials such as 28 into olefins, and the demonstration that phenyl ...