Synthetic studies of bioactive marine polycyclic ethers

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The marine polycyclic ether toxins, associated with the massive fish kills and human food poisoning from red tides and dinoflagellates have attracted much attention in the chemistry community for their intriguing molecular structure and biological activity. In this project, synthetic studies of adriatoxin and gambierol were undertaken, and the following results were obtained.1.Synthetic studies of adriatoxin.Adriatoxin, a diarrheic shellfish toxin isolated from mussels, consists of a decacyclic polyether framework containing three sulfate esters and a side chain. The ABCDEF ring system was synthesized in a convergent manner by coupling of the A and DEF rings which were prepared based on an oxiranyl anion strategy. On the other hand, the HIJ ring fragment was constructed by oxiranyl anion chemistry and radical cyclization.2.Synthetic studies of gambierol.Gambierol is a neurotoxin isolated from the ciguatera causative dinoflagellate Gambierdiscus toxicus. The structure consists of an octacyclic polyether containing three hydroxy groups and a partially skipped triene side chain. The ABCD ring system of gambierol has synthesized in 21 synthetic transformations starting from monocyclic D ring diol. The key reactions employed were alkylation of oxiranyl anion, 6-endo cyclization, dithiane-epoxide coupling reaction, and reductive etherification.