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Stereospecific cleavage of carbon‐phosphorus bonds: Stereochemical course of the phosphinoyl curtius (harger) reaction
Author(s) -
Denmark Scott E.,
Dorow Roberta L.
Publication year - 2002
Publication title -
chirality
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.43
H-Index - 77
eISSN - 1520-636X
pISSN - 0899-0042
DOI - 10.1002/chir.10062
Subject(s) - chemistry , diastereomer , stereocenter , curtius rearrangement , stereospecificity , azide , walden inversion , enantiopure drug , asymmetric carbon , stereochemistry , medicinal chemistry , methanol , carbon fibers , nitrogen , organic chemistry , optically active , catalysis , enantioselective synthesis , materials science , composite number , composite material
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). Chirality 14:241–257, 2002.© 2002 Wiley‐Liss, Inc.