Brønsted Base-Catalyzed Umpolung Intramolecular Cyclization of Alkynyl Imines

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Abstract

A novel “umpolung” intramolecular cyclization of alkynyl imines, in which the electrophilic imine sp2-carbon formally serves as a nucleophilic site, was developed under Brønsted base catalysis. The reaction involves the unprecedented catalytic generation of α-aminoester enolates from α-iminoesters via the 1,2-addition of the anion of a secondary phosphite to an imine moiety followed by the [1,2]-rearrangement of a dialkoxyphosphoryl moiety from carbon to nitrogen, which is a formal umpolung process, and the intramolecular addition to an alkyne. This is a rare example of a [1,2]-rearrangement of a dialkoxyphosphoryl moiety from carbon to nitrogen to generate an α-amino carbanion and the first catalytic carbon–carbon bond forming reaction utilizing the resulting carbanion as a nucleophile.

Original languageEnglish
Pages (from-to)3998-4001
Number of pages4
JournalChemistry - A European Journal
Volume24
Issue number16
DOIs
Publication statusPublished - 2018 Mar 15

Keywords

  • Brønsted base catalysis
  • intramolecular cyclization
  • organocatalysts
  • rearrangement
  • umpolung

ASJC Scopus subject areas

  • Catalysis
  • Organic Chemistry

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