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

<p></p> <p>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 <i>H</i>-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 <i>P</i>-chiral [<sup>16</sup>O,<sup>17</sup>O,<sup>18</sup>O]phosphoenol pyruvates.</p>