Unconventional Fragment Usage Enables a Concise Total Synthesis of (−)-Callyspongiolide

An asymmetric synthesis of (−)-callyspongiolide is described. The route builds the macrolide domain atypically from a disaccharide and a monoterpene without passing through a seco-acid. Chiral iridium catalysis selectively joins fragments. Subsequent degradation of an imbedded butyrolactone via perh...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2018-01, Vol.140 (4), p.1280-1284
Main Authors: Manoni, Francesco, Rumo, Corentin, Li, Liubo, Harran, Patrick G.
Format: Article
Language:English
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Summary:An asymmetric synthesis of (−)-callyspongiolide is described. The route builds the macrolide domain atypically from a disaccharide and a monoterpene without passing through a seco-acid. Chiral iridium catalysis selectively joins fragments. Subsequent degradation of an imbedded butyrolactone via perhemiketal fragmentation affords a stereo- and regio-defined homoallylic alcohol that is engaged directly in a carbonylative macrolactonization. Further elaboration of the polyunsaturated appendage provides the natural product in a particularly direct and flexible manner.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.7b13591