Total Synthesis of Solandelactones E and F, Homoeicosanoids from the Hydroid Solanderia secunda

Asymmetric total syntheses of solandelactones E and F confirmed that hydroxyl configuration at C11 in these oxylipins had been misassigned and that the stereochemistry at this center should be reversed. Key steps in the synthesis involved a Nagao asymmetric acetate aldol reaction, a directed Simmons−Smith cyclopropanation, a Holmes−Claisen rearrangement to establish the unsaturated octalactone, and a Nozaki−Hiyama−Kishi coupling to connect two major fragments at C11−C12.