Highly Selective One-Pot Synthesis of Spirophosphoranes Exhibiting Reversed Apicophilicity by Oxidation of Dianions Generated from P−H Spirophosphorane

[see reaction]. Mild and highly selective one-pot procedures for obtaining phosphoranes that exhibit reversed (O-cis) apicophilicity are described. On the basis of the procedures, O-cis phosphorane bearing an aryl group (R = 2,4,6-tri-i-propylphenyl) could be isolated for the first time; the procedure is also applicable for alkyl derivatives. Particularly effective was the use of I2 as an oxidizing reagent.