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Total Syntheses Of Spiroviolene And Spirograterpene A: A Structural Reassignment With Biosynthetic Implications

Hyungmin Chi, Charles Cole, Pengfei Hu, Cooper A Taylor, S. Snyder
Published 2020 · Chemistry

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The recent natural product isolates spiroviolene and spirograterpene A are two relatively non-functionalized linear triquinane terpenes with a large number of structural homologies. Nevertheless, three significant areas of structural disparity exist based on their original assignments, one of which implies a key stereochemical divergence early in their respective biosyntheses. Herein, using two known bicyclic ketone intermediates, a core Pd-catalyzed Heck cyclization sequence, and several chemoselective transformations, we describe concise total syntheses of both natural product targets and propose that the structure of spiroviolene should be reassigned. As a result, these natural products possess greater homology than previously anticipated.
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