N-heterocyclic carbene catalyzed synthesis of d-sultones via a,b-unsaturated sulfonyl azolium intermediates

Andrei Ungureanu, Alison Levens, Lisa Candish, David Lupton

Research output: Contribution to journalArticleResearchpeer-review

33 Citations (Scopus)

Abstract

A limited array of reactive intermediates have enabled a wealth of discoveries in N-heterocyclic carbene organocatalysis. In this study, the viability of α,β-unsaturated sulfonyl azoliums as double electrophiles in new reactions is examined. Specifically, the (3+3) annulation of such species with the trimethylsilyl enol ethers of various 1,3-dicarbonyl compounds has been developed. This reaction provides access to a range of novel unsaturated δ-sultones (18 examples) in good yields (40-88 %) under mild reaction conditions. Mechanistic studies and the development of an enantioselective variant (55 % yield, 73:27 e.r.) support the intermediacy of an α,β-unsaturated sulfonyl azolium species. A new intermediate: The coupling of α,β-unsaturated sulfonyl fluorides with silyl enol ethers in the presence of N-heterocyclic carbenes provides δ-sultones in good yields. Various mechanistic studies indicate the formation of an α,β-unsaturated sulfonyl azolium intermediate
Original languageEnglish
Pages (from-to)11780-11784
Number of pages5
JournalAngewandte Chemie - International Edition
Volume54
Issue number40
DOIs
Publication statusPublished - 2015

Keywords

  • N-heterocyclic carbenes
  • nucleophilic catalysis
  • organocatalysis
  • sulfonyl azolium intermediates
  • sulfonyl fluorides

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