Stereospecific cleavage of carbon-phosphorus bonds: Stereochemical course of the phosphinoyl curtius (harger) reaction

Research output: Contribution to journalArticlepeer-review

Abstract

The homochiral phosphinic azides (R,R)-1 and (S,S)-1 were prepared in enantiomerically pure form by resolution of diastereomeric phosphinamides derived from (S)-1-phenylethylamine and (R)-phenylglycine. Irradiation of the azides in methanol induced a photo-Curtius rearrangement to phosphonamidates in which the stereogenic carbon unit migrated to a nitrogen atom. Hydrolysis of the phosphonamidates produced 1-phenylethylamine, which was 99.0% e.e. and of the same configuration as the carbon unit in the starting azide (99.0% retention).

Original languageEnglish (US)
Pages (from-to)241-257
Number of pages17
JournalChirality
Volume14
Issue number2-3
DOIs
StatePublished - 2002

Keywords

  • Carbon-phosphorus bond cleavage
  • Curtius reaction
  • Phosphinoyl azides
  • Stereospecificity

ASJC Scopus subject areas

  • Analytical Chemistry
  • Catalysis
  • Pharmacology
  • Drug Discovery
  • Spectroscopy
  • Organic Chemistry

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