Total synthesis of nominal gobienine A

Azusa Kondoh, Alexander Arlt, Barbara Gabor, Alois Fürstner

Research output: Contribution to journalArticle

23 Citations (Scopus)

Abstract

The lichen-derived glycoconjugate gobienine A is structurally more complex than most glycolipids isolated from higher plants by virtue of the all-cis substituted γ-lactone substructure embedded into its macrocyclic frame. A concise entry into this very epimerization-prone and hence challenging structural motif is presented, which relies on an enantioselective cyanohydrin formation, an intramolecular Blaise reaction, a palladium-catalyzed alkoxycarbonylation, and a diastereoselective hydrogenation of the tetrasubstituted alkene in the resulting butenolide. This strategy, in combination with ring-closing olefin metathesis for the formation of the macrocyclic perimeter, allowed the proposed structure of gobienine A (1) to be formed in high overall yield. The recorded spectral data show that the structure originally attributed to gobienine A is incorrect and that it is not the epimerization-prone ester site on the butanolide ring that is the locus of misassignment; rather, the discrepancy must be more profound.

Original languageEnglish
Pages (from-to)7731-7738
Number of pages8
JournalChemistry - A European Journal
Volume19
Issue number24
DOIs
Publication statusPublished - 2013 Jun 10
Externally publishedYes

Keywords

  • butanolides
  • carbonylation
  • glycolipids
  • metathesis
  • natural products
  • total synthesis

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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