Conformational properties of diastereomeric 5′-O-DMT-2′Deoxythymidine 3′-O-(S-methyl-methanephosphonothiolate)s and -(Se-methyl-methanephosphonoselenolate)s in solution as studied by NMR methods

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Abstract

Stereochemical characterization of diastereomerically pure 5′-O-DMT-2′deoxythymidine 3′-O- (S-methyl-methanephosphonothiolate) s and - (Se-methyl-methane-phosphono-selenolate)s by NMR methods are reported. 1H-1H, 1H-31P, and 13c-31P coupling constants and nuclear overhauser enhancement (NOE) connectivities from transverse cross-relaxation experiments in rotating frame (T-ROESY) were measured to correlate the conformational properties of the isomers with the absolute configrations at the phosphorus obtained from X-ray studies of the relatives of Sp configured isomers. Conformational differences between the stereoisomers were found to be restricted to the different orientation of the C3′-O3′-P bond. The NMR data reflected the preferred ε- conformation for the Sp isomers, while in the Rp isomers the conformational equilibrium was shifted toward the εt domain. These results also indicated that for 5′-protected mononucleotides the absolute configuration at the phosphorus atom can be inferred from the NOE experiments and the trends observed in vicinal carbon-phosphorus coupling constants.

Original languageEnglish
Pages (from-to)675-680
Number of pages6
JournalChirality
Volume12
Issue number9
DOIs
Publication statusPublished - Dec 1 2000

Keywords

  • Modified nucleotides
  • ROESY spectra
  • Vicinal C-P couplings

ASJC Scopus subject areas

  • Analytical Chemistry
  • Catalysis
  • Pharmacology
  • Drug Discovery
  • Spectroscopy
  • Organic Chemistry

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