Synthesis of Racemic Fomannosin and Illudol Using a Biosynthetically Patterned Common Intermediate

M. F. Semmelhack, Shuji Tomoda, Hiroto Nagaoka, Susan D. Boettger, Kenneth M. Hurst

Research output: Contribution to journalArticlepeer-review

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Abstract

The synthesis of fomannosin, a toxic fungal metabolite with a unique methylenecyclobutene structure, is approached in two different ways, making use of rigid tricyclic intermediates to control the configuration at two crucial chiral centers. The first approach was carried through the formation of the cyclobutane ring, using cycloaddition of ethoxyacetylene to a ketene. The stereoselectivity was disappointing, and that strategy was abandoned in favor of an approach which derived from the biosynthesis pathway for fomannosin. In this route, the Diels-Alder reaction of a cyclobutenecarboxylate with the appropriate diene generates the tricyclic protoilludane skeleton stereospecifically. The Diels-Alder adduct is converted through a series of eight steps to racemic illudol, a natural protoilludane sesquiterpene, and through 11 steps to result in the first total synthesis of fomannosin.

Original languageEnglish (US)
Pages (from-to)747-759
Number of pages13
JournalJournal of the American Chemical Society
Volume104
Issue number3
DOIs
StatePublished - Jan 1 1982

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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