Gold-catalyzed cycloisomerization of 1,6,8-dienyne carbonates and esters to cis-cyclohepta-4,8-diene-fused pyrrolidines

Weidong Rao, Sally, Stuart Neil Berry, Philip Wai Hong Chan

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33 Citations (Scopus)

Abstract

A synthetic approach that provides access to ciscyclohepta-4,8-diene-fused pyrrolidines efficiently through AuI-catalyzed cycloisomerization of 1,6,8-dienyne carbonates and esters at a low catalyst loading of 2 mol% is reported. Starting carbonates and esters with a pendant alkyl group on the terminal alkenyl carbon center were found to favor tandem 1,2-acyloxy migration/cyclopropanation followed by Cope rearrangement of the resulting cis-3-azabicyclo- [3.1.0]hexane intermediate. On the other hand, substrates containing a terminal diene or starting materials in which the distal alkene moiety bears a phenyl substituent were observed to undergo competitive but reversible 1,3-acyloxy migration prior to the nitrogen-containing bicyclic ring formation. The delineated reaction mechanism also provides experimental evidence for the reversible interconversion between the oft-proposed organogold intermediates obtained in this step of the tandem process.
Original languageEnglish
Pages (from-to)13174 - 13180
Number of pages7
JournalChemistry - A European Journal
Volume20
Issue number41
DOIs
Publication statusPublished - 2014
Externally publishedYes

Keywords

  • Gold
  • gold catalysis
  • Catalysis

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