Stereochemistry of electrophilic and nucleophilic substitutions at phosphorus

Abstract Nucleophilic and electrophilic substitutions are the most often applied reactions in organophosphorus chemistry. They are closely interrelated, because in a reacting pair always one reagent is an electrophile, and another nucleophile. The reactions of electrophilic and nucleophilic substitutions at the phosphorus center proceed via the formation of a pentacoordinated intermediate. The mechanism of nucleophilic substitution involves the exchange of ligands in the pentacoordinate phosphorane intermediate, leading to the more stable stereomer under the thermodynamic control. Electrophilic substitution proceeds with retention of absolute configuration, whereas nucleophilic substitution with inversion of configuration at the phosphorus center.