title: Stereospecific cleavage of carbon-phosphorus bonds: stereochemical course of the phosphinoyl curtius (Harger) reaction.
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)-l-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).
authors.affiliation: Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, Illinois 61801, USA.
authors.forename: Scott E
authors.initials: SE
authors.lastname: Denmark
authors.forename: Roberta L
authors.initials: RL
authors.lastname: Dorow