Tandem enyne metathesis and Claisen rearrangement: A versatile approach to conjugated dienes of variable substitution patterns

Daniel A. Clark, Amol A. Kulkarni, Kyle Kalbarczyk, Bryan Schertzer, Steven T. Diver

Research output: Contribution to journalArticle

37 Scopus citations

Abstract

To extend the versatility of the ruthenium carbene-promoted enyne metathesis, it was combined with an Ireland ester enolate Claisen rearrangement. This reaction sequence provided conjugated dienes of higher substitution pattern than that obtained through a cross-enyne metathesis alone. The Ireland-Claisen was conducted across both acyclic and cyclic dienes produced from cross-metathesis and methylene-free enyne metathesis, respectively. In the case of cyclodienes, the Ireland-Claisen rearrangement produced s-trans locked dienes which underwent mode-selective ene reaction. The tandem, sequential use of the Ireland-Claisen rearrangement also proved suitable for chirality transfer originating from chiral propargylic alcohols. Last, the tandem metathesis/Ireland-Claisen was utilized to access 4-substituted-3,5- cyclohexadiene diol derivatives, which are valuable chiral intermediates for natural product synthesis. The combination of this pericyclic reaction with a catalytic metathesis reaction extends the versatility of cross-metathesis since additional diene motifs can be accessed.

Original languageEnglish (US)
Pages (from-to)15632-15636
Number of pages5
JournalJournal of the American Chemical Society
Volume128
Issue number49
DOIs
StatePublished - Dec 13 2006

ASJC Scopus subject areas

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

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