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Updated: May 29, 2026

Synthesis of High Purity Nonsymmetric Dialkylphosphinic Acid Extractants
Published on: October 19, 2017
31P NMR and computational studies on stereochemistry of conversion of phosphoramidate diesters into the corresponding
Linda Söderberg1, Gaston Lavén, Marcin Kalek
1Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, Stockholm, Sweden.
Abstract:
31P NMR spectroscopy was used to investigate a stereochemical course of a nitrite-promoted conversion of phosphoramidate diesters into the corresponding phosphotriesters. It was found that this reaction occurred with almost complete epimerization at the phosphorus center and at the C1 atom in the amine moiety. On the basis of the 31P NMR data, a plausible mechanism for the reaction was proposed. The density functional theory calculation of the key step of the reaction, i.e., breaking of the P-N bond and formation of the P-O bond, suggested a one-step S(N)2(P) process with retention of configuration at the phosphorus center.
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