✦ LIBER ✦
Stereospecific cleavage of carbon-phosphorus bonds: Stereochemical course of the phosphinoyl curtius (harger) reaction
✍ Scribed by Scott E. Denmark; Roberta L. Dorow
- Publisher
- John Wiley and Sons
- Year
- 2002
- Tongue
- English
- Weight
- 261 KB
- Volume
- 14
- Category
- Article
- ISSN
- 0899-0042
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✦ Synopsis
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). Chirality 14:241–257, 2002.© 2002 Wiley‐Liss, Inc.