gpss_a_1452235_sm7911.doc (812.5 kB)

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

Download (812.5 kB)
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.

Funding

Austrian Science Fund (P19869-N19).

History

Licence

Exports