Reinvestigation of the Substitutions Reaction of Stereogenic Phosphoryl Compounds: Stereochemistry, Mechanism, and Applications

摘要: Nucleophilic substitutions at P centers are of high importance in biological processes and asymmetric synthesis. However, detailed studies on this topic rare. P-Stereogenic compounds containing P–Cl, P–O, P–S bonds were diastereoselectively prepared then used to study the substitution Cl, O, S phosphorus with organometallic reagents. It was proposed that alkynyl metallic reagents an SN2-like mechanism (route A1) a Berry pseudorotation (BPR) pentacoordinated intermediates B1) involved afforded P-inverted P-retained products, respectively. The conversion P–Cl functionality P–C can be controlled by either temperature or order addition starting materials. introduction bond using alkyl reagent proceeded through routes A2 A2′. At higher temperatures, products predominantly via route A2. lower bis-substituted...