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DOI: 10.1055/s-0033-1340357
Synthesis of (+)-Fusarisetin A
Publication History
Publication Date:
13 December 2013 (online)
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Significance
Isolated in 2011 from the soil fungus Fusarium sp. FN080326, fusarisetin A has gained considerable attention because of its unprecedented molecular structure and its striking bioactivity. Fusarisetin A exhibits a complex 6,6,5,5,5-fused pentacyclic ring system containing ten stereocenters. Moreover, this natural product displays potent inhibition of acinar morphogenesis, cell migration, and invasion in MDA-MB-231 breast cancer cells, without apparent cytotoxicity. Li, Yang, and co-workers report a total synthesis of (+)-fusarisetin A based on a stereoselective intramolecular Pauson–Khand reaction for the construction of the 6,6,5-tricyclic moiety.
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Comment
After screening of conditions, the authors identified the Co2(CO)8-mediated Pauson–Khand reaction as the most efficient method for the stereoselective formation of cyclopentenone B. Stereoselective reduction of B proved to be challenging. Thus, installation of a mesylate group followed by desilylation was crucial to access ketone C with the correct configuration at C6 and C7. Carbonylative esterification afforded ester D, which was further elaborated into amide E. Finally, Dieckmann condensation followed by hemiacetalization furnished (+)-fusarisetin A along with the separable diastereoisomer F (dr = 3:2).
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