The α-hydroxyphosphonate-phosphate rearrangement of a noncyclic substrate – some new observations
Literature Information
Susanne Prechelmacher, Kurt Mereiter, Friedrich Hammerschmidt
Racemic ethyl hydrogen (1-hydroxy-2-methylsulfanyl-1-phenylethyl)phosphonate was resolved with (R)-1-phenylethylamine. The (R)-configuration of the (−)-enantiomer was determined by chemical correlation. Esterification of the (−)-enantiomer with a substituted diazomethane derived from 3-hydroxy-1,3,5(10)-estratrien-17-one delivered two epimeric phosphonates separated by HPLC. Methylation with methyl fluorosulfate at the sulfur atom and treatment with a strong base induced an α-hydroxyphosphonate-phosphate rearrangement with formation of dimethyl sulphide and two enantiomerically pure enol phosphates. Their oily nature interfered with a single crystal X-ray structure analysis to determine the stereochemistry at the phosphorus atom.
Related Literature
Royal Agricultural Society of England. Annual Report of the Consulting Chemist for 1940
DOI: 10.1039/AN941660334A
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Organic & Biomolecular Chemistry

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