The Stereochemical Course of Migration from Phosphorus to Nitrogen in the Photo-Curtius Rearrangement of Phosphinic Azides (Harger Reaction)

Scott E Denmark, Roberta L. Dorow

Research output: Contribution to journalLetter

Abstract

The homochiral phosphinic azides (R,R) -1 and (S,S)-1 have been prepared in enantiomerically pure form by resolution of diastereomeric phosphinamides derived from (S)-l-phenylethylamine and (R)-phenylglycine. Irradiation of the azides in methanol induced a photo-Curtius rearrangement of phosphonamidates in which the stereogenic carbon unit migrated to a nitrogen atom. Hydrolysis of the phosphonamidates produced 1-phenylethylamine, which was 99.0% ee and of the same configuration as the carbon unit in the starting azide (99.0% net retention). The implication for asymmetric synthetic methodology is discussed.

Original languageEnglish (US)
Pages (from-to)5-6
Number of pages2
JournalJournal of Organic Chemistry
Volume54
Issue number1
DOIs
StatePublished - Jan 1 1989

ASJC Scopus subject areas

  • Organic Chemistry

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