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Published on: May 25, 2016
The α-hydroxyphosphonate-phosphate rearrangement of a noncyclic substrate - some new observations
Susanne Prechelmacher1, Kurt Mereiter2, Friedrich Hammerschmidt1
1Institute of Organic Chemistry, University of Vienna, Währingerstrasse 38, A-1090 Vienna, Austria. friedrich.hammerschmidt@univie.ac.at.
Abstract:
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.
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