The case for the intermediacy of monomeric metaphosphate analogues during oxidation of H-phosphonothioate, H-phosphonodithioate, and H-phosphonoselenoate monoesters: mechanistic and synthetic studies.
Studies on the reaction of H-phosphonothioate, H-phosphonodithioate, and H-phosphonoselenoate monoesters with iodine in the presence of a base led to identification of a unique oxidation pathway, which consists of the initial oxidation of the sulfur or selenium atom in these compounds, followed by oxidative elimination of hydrogen iodide to generate the corresponding metaphosphate analogues. The intermediacy of the latter species during oxidation of the investigated H-phosphonate monoester derivatives with iodine was supported by various diagnostic experiments. The scope and limitation of these oxidative transformations for the purpose of the synthesis of nucleoside phosphorothioate, nucleoside phosphorodithioate, and nucleoside phosphoroselenoate diesters was also investigated.
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, S-106 91 Stockholm, Sweden.
Agnieszka
A
Bartoszewicz
Marcin
M
Kalek
Jacek
J
Stawinski
D063065:Organophosphonates / Q000737:chemistry*; D010084:Oxidation-Reduction; D010757:Phosphorous Acids / Q000737:chemistry*; D018036:Selenium Compounds / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000737:chemistry*
D063065:Organophosphonates; D010757:Phosphorous Acids; D018036:Selenium Compounds; D013438:Sulfhydryl Compounds; C043639:metaphosphoric acid