Synthesis,Crystal Structure,and Diastereomeric Transfer of Pentacoordinated Phosphoranes Containing Valine or Iso-Leucine Residue

Pentacoordinated phosphoranes containing valine or iso-leucine residue (2-phenyl-2,7⁵-spiro[1,3,2-phenanthrodioxaphosphole-2,2′-1,3,2-oxazaphospholan]-5′-one) were synthesized through sequential two-step reactions, whereby the reaction products of phenyldichlorophosphine with N,O-bis(trimethylsilyl)valine or iso-leucine were followed by the addition of phenanthrenequione, and the crystals of 4a and 4b were obtained from benzene and hexane mixed solution. The x-ray structure of the crystals 4a and 4b revealed that they are distorted TBP, exhibiting R_P absolute configuration. The ³¹P NMR spectra showed that the S_P diastereomer could transfer into the other one R_P that came out from the solution during crystallization. Correspondingly, when it was dissolved in solvents the R_P diastereomer transferred into the other one S_P, and the pair of diastereomers changed each other in solution at room temperature through a phosphonium carboxylate zwitterions intermediate.