Organic Chemistry

Stereodivergent Total Syntheses of (+)-Mycaperoxides C, D, G Methyl Ester and (-)-Mycaperoxide B

Authors

Abstract

Mycaperoxides are natural endoperoxides isolated from different Mycale genus sponges, showing significant antiviral or antibacterial activities. We report herein the first total syntheses of representative congeners of this family from sclareol using a stereodivergent approach. Thus, an innovative oxidative ring expansion of cyclobutanol was used to bring the 1,2-dioxane subunit, and a Mukaiyama aldol reaction on peroxycarbenium species was utilized to install the propionic acid subunit. During the study toward (+)-mycaperoxide D methyl ester (2), the isolation of the eight possible diastereomers under their ethyl thioester form allowed to build a pertinent database for further NMR assignment studies. Thus, we completed the total syntheses of (+)-mycaperoxides D, C, G methyl ester, and (-)-mycaperoxide B in 11 to 15 steps, confirming their origi-nal assignment.

Version notes

Updated the supporting information. The copies of spectra were missing because of a wrong file.

Content

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Supplementary material

Thumbnail image of Supporting Information-ChemXriv.pdf
SUPPORTING INFORMATION
General information, detailed experimental procedures, characterization data, cartesian coordinates of 16h, and copies of 1H and 13C NMR spectra of all compounds.