Synthesis of nucleoside phosphorothio-, phosphorodithio- and phosphoroselenoate diesters via oxidative esterification of the corresponding H-phosphonate analogues.
It was found that nucleoside H-phosphonothioate, H-phosphonodithioate, and H-phosphonoselenoate monoesters in the presence of iodine underwent rapid oxidative esterification with various hydroxylic components to produce in "one pot" reactions the corresponding nucleoside phosphorothioate, nucleoside phosphorodithioate and nucleoside phosphoroselenoate diesters in good yields. The transformation represents a novel alternative method for the synthesis of internucleotide phosphate bridge, bearing sulfur or selenium atoms. Mechanistic studies have revealed metaphosphate analogues as the probable intermediates, involved in the reactions.
Kalek
Marcin
M
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, S-106 91 Stockholm, Sweden.
Bartoszewicz
Agnieszka
A
Stawinski
Jacek
J
D004951:Esterification; D007455:Iodine / Q000737:chemistry; D009705:Nucleosides / Q000138:chemical synthesis* / Q000737:chemistry; D063065:Organophosphonates / Q000737:chemistry*; D016566:Organoselenium Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010084:Oxidation-Reduction; D013872:Thionucleosides / Q000138:chemical synthesis* / Q000737:chemistry
D009705:Nucleosides; D063065:Organophosphonates; D016566:Organoselenium Compounds; D013872:Thionucleosides; D007455:Iodine