A Highly Stereoselective and Completely Regiospecific Method for the Dehydration of β-Hydroxy Esters via β-Alanoxy Enolates. Application to the Synthesis of Trisubstituted Olefins and Two Ant Mandibular Gland Secretions

John A. Katzenellenbogen, Thanin Utawanit

Research output: Contribution to journalArticlepeer-review

Abstract

The treatment of a β-hydroxy ester with aluminum ethoxide or diethoxyaluminum chloride, followed by warming with added lithium diisopropylamide, produces the corresponding α,β-unsaturated ester in moderate yield (44-56%). This process is completely regiospecific (no β, isomers formed) and in suitably substituted cases is completely stereospecific, producing only the E olefin isomer. It is conceived that the reaction proceeds through a β-alanoxy enolate intermediate, similar to that postulated in the lithium aluminum hydride reduction of β-dicarbonyl enolates; the stereoselectivity results from the minimization of 1,4 interactions in a boat cyclohexane-like transition state. This alanoxy enolate dehydration process has been applied in the stereo- and regiospecific syntheses of two ant mandibular gland secretions.

Original languageEnglish (US)
Pages (from-to)6153-6158
Number of pages6
JournalJournal of the American Chemical Society
Volume96
Issue number19
DOIs
StatePublished - Sep 1 1974

ASJC Scopus subject areas

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

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