Spirooxyphosphoranes with quintuply-connected phosphorus were made from the reaction of phenanthrenequinone, benzil, biacetyl, and 1-phenylpropanedione with 5-membered and 6-membered cyclic phosphite esters and amides. The P31 NMR spectra were compared with those of the oxyphosphoranes derived from open-chain trimethyl and triphenyl phosphites. Further comparisons were made with spiroaminooxyphosphoranes