31P NMR and Computational Studies on Stereochemistry of Conversion of Phosphoramidate Diesters into the Corresponding Phosphotriesters |
| |
| Authors: | Linda Söderberg Gaston Lavén Marcin Kalek Professor Jacek Stawinski |
| |
| Affiliation: | 1. Department of Organic Chemistry, Arrhenius Laboratory , Stockholm University , Stockholm , Sweden;2. Department of Organic Chemistry, Arrhenius Laboratory , Stockholm University , Stockholm , Sweden;3. Institute of Bioorganic Chemistry, Polish Academy of Sciences , Poznan , Poland |
| |
| 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 SN2(P) process with retention of configuration at the phosphorus center. |
| |
| Keywords: | Phosphoramidates nitrite-promoted rearrangement phosphotriesters DFT calculations edge attack SN2(P) |
|
|
