Asymmetric Michael Addition of Malonates to Enones Catalyzed by an α- D -Glucopyranoside-Based Crown Ether

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Abstract

The chiral monoaza-15-crown-5 lariat ether annelated to methyl-4,6-O-benzylidene-α-d-glucopyranoside has been applied as a phase-transfer catalyst in several Michael addition reactions under mild conditions affording the adducts with good to excellent enantioselectivities. In the addition of α-substituted diethyl malonates to trans-chalcones, the substituents of the reactants had a significant impact on the yield and enantioselectivity. Among the reactions of substituted diethyl malonates, that of diethyl-2-acetoxymalonate gave the best results (up to 97% ee). New phase-transfer-catalyzed cyclopropanation reactions (MIRC reactions) of a few enones were also developed using diethyl 2-bromomalonate as the nucleophile. The corresponding chiral cyclopropane derivatives were formed with enantioselectivities up to 92% from 2-benzylidenemalononitrile starting materials, in up to 60% enantiomeric excess using 2-benzylidene-1,3-diphenyl-1,3-propanediones, and in up to 88% optical purity applying trans-chalcones as the starting materials.

Original languageEnglish
Article numberst-2015-b0142-l
Pages (from-to)1847-1851
Number of pages5
JournalSynlett
Volume26
Issue number13
DOIs
Publication statusPublished - Aug 12 2015

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Keywords

  • asymmetric Michael reactions
  • asymmetric cyclopropanations
  • enantioselectivity
  • phase-transfer catalysis
  • sugar-based crown ethers

ASJC Scopus subject areas

  • Organic Chemistry

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