We describe the total synthesis of (+)-coriamyrtin, which bears a highly functionalized cis-hydrindane skeleton and is a widely known neurotoxin of the Coriariaceae family. Our synthetic strategy involves the highly stereoselective construction of the cishydrindane skeleton via a desymmetrizing strategy involving a 1,3cyclopentanedione moiety using an intramolecular aldol reaction and the formation of the 1,3-diepoxide moiety of coriamyrtin through the elaborate functionalization of the cyclopentane ring in the bicyclic structure. P icrotoxane-type sesquiterpenes are widely distributed in plants, such as Coriariaceae, Orchidaceae, and Menispermaceae. 1 Since picrotoxin, which is a poisonous compound composed of a 1:1 mixture of picrotoxinin (1) and picrotin (2), was found in Menispermum cocculus in 1818, more than 130 picrotoxane-type natural products have been isolated (Figure 1). 2 Because 1 is a strong antagonist of the γ-

This paper describes the total synthesis of (+)-coriamyrtin, a picrotoxane-type sesquiterpene. The natural product is widely known as a neurotoxin of the Coriariaceae family and bears a highly functionalized cis-hydrindane skeleton. Despite being biologically and synthetically attractive molecule, only two examples of the total synthesis are reported to date. Our synthetic strategy involves the highly stereoselective construction of the cis-hydrindane skeleton via the desymmetric strategy of a 1,3-cyclopentanedione moiety using an intramolecular aldol reaction and elaborate functionalization of the cyclopentane ring in the bicyclic structure for the formation of the 1,3-diepoxide moiety of coriamyrtin. Our method could be applied to synthesize various natural products with similar bicyclic skeletons and to expand neurobiological studies using synthesized products.