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Formal synthesis of P-chiral [16O,17O,18O]phosphoenol pyruvates by means of the α-hydroxyphosphonate-phosphate rearrangement

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journal contribution
posted on 13.03.2018, 19:09 by Petra Malová Križková, Alexander Roller, Friedrich Hammerschmidt

Transesterification of tris(hexafluoroisopropyl) phosphite with racemic 3-methyl-1-phenyl-butane-1,3-diol gave two isomeric hexafluoroisopropyl-substituted 1,2,3-dioxaphosphinanes. These cyclic phosphites were hydrolyzed rapidly and enantioselectively by water catalyzed by HCl. The respective metalated H-phosphonates were added to ethyl 3-chloropyruvate and underwent a stereospecific α-hydroxyphosphonate-phosphate rearrangement to protected phosphoenol pyruvates. This sequence with oxygen isotope-labeled enantiomers represents an alternative approach to P-chiral [16O,17O,18O]phosphoenol pyruvates.


Austrian Science Fund (P19869-N19).