Synthesis and Characterization of New Pyrospirophosphoranes Containing a P-O-P Bond by the Atherton-Todd Reaction

The classical Atherton-Todd reaction has been successfully applied to the synthesis of pentacoordinate pyrospirophosphoranes containing a P-O-P bond under mild conditions. The absolute configurations of the products were confirmed by X-ray diffraction analysis and spectroscopic identification. And P-31 NMR chemical shifts of the products were correlated with stereochemistry. A possible mechanism for explaining the stereochemistry of the reaction was proposed, and it could well explain the results of the reactions of different pentacoordinate hydrospirophosphoranes.