Oxidopyrylium ylide, which can be prepared from furfuryl alcohol, readily dimerizes in the regio- and stereoselective manner generating doubly bridged carbocycle. Although this dimer is a potential precursor of highly functionalized cyclooctanoids, its application to natural product synthesis has never been reported until today.
We accomplished the first total synthesis of Jujuyane, a sesquiterpene lactone isolated from Stevia jujuyansis, utilizing oxidopyrylium dimerization reaction. Stereocenters around a core 8-membered ring structure could be settled by substrate-controlled reactions on the oxa-bridged synthetic intermediate. Subsequent oxa-bridge opening and functional group manipulation completed the total synthesis of Jujuyane.
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