Enantioselective synthesis of α,α-disubstituted cyclopentenes by an N-heterocyclic carbene-catalyzed desymmetrization of 1,3-diketones

Manabu Wadamoto, Eric M. Phillips, Troy E. Reynolds, Karl A. Scheidt*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

184 Scopus citations

Abstract

The enantioselective synthesis of α,α-disubstituted cyclopentenes using N-heterocyclic carbene catalysis is reported. This desymmetrization reaction proceeds via a chiral enol generated in situ from the combination of an enantiopure azolium salt and α,β-unsaturated aldehyde. This reactive enol undergoes addition to one of two enantiotopic ketones to afford an optically active β-lactone after the intermediate carbinol is involved in an internal acylation event to release the carbene catalyst. In the substrates where R = aryl, a decarboxylation occurs immediately after lactone formation to produce the quaternary center-containing cyclopentene products in up to 96% ee. When the R group is alkyl, the β-lactones are isolated in moderate yield and high diastereo- and enantioselectivity.

Original languageEnglish (US)
Pages (from-to)10098-10099
Number of pages2
JournalJournal of the American Chemical Society
Volume129
Issue number33
DOIs
StatePublished - Aug 22 2007

ASJC Scopus subject areas

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

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