Article: Direct assignment of the absolute configuration of a distinct class of deoxyribonucleoside cyclic N-acylphosphoramidites at phosphorus by M-GOESY nuclear magnetic resonance spectroscopy.
Journal of the American Chemical Society
2002 Volume 124, Issue 7, Page(s) 1180–1181
Abstract: ... is easily accomplished with computer-assisted molecular modeling and M-GOESY NMR spectroscopy ... interaction between benzylic H-5 and sugar H-2' ', which can predictably be detected by M-GOESY NMR in SP-3 ... predictions, M-GOESY NMR spectra of SP-3 and RP-3 revealed NOE signals generated from nuclei near ...
Abstract | The determination of the absolute configuration of deoxyribonucleoside cyclic N-acylphosphoramidites at phosphorus toward the synthesis of P-stereodifined phosphorothioated oligodeoxyribonucleotides is easily accomplished with computer-assisted molecular modeling and M-GOESY NMR spectroscopy. Specifically, computer-modeling diasteromeric phosphoramidite 3 has identifed a proximal (2.55 A) through-space interaction between benzylic H-5 and sugar H-2' ', which can predictably be detected by M-GOESY NMR in SP-3 but not in RP-3 because of being too distant (5.85 A). Consistent with computer-assisted modeling predictions, M-GOESY NMR spectra of SP-3 and RP-3 revealed NOE signals generated from nuclei near the selectively excited H-2' ' that are common to both SP-3 and RP-3, namely those of H-2', H-4', H-3', and H-1'. In addition, a diagnostic NOE signal at 5.5 ppm (benzylic H-5) is, as predicted, only detected in SP-3 and thus provides an unequivocal assessment of the configuration of the diastereomer at phosphorus. M-GOESY NMR data also confirm that the condensation of deoxyribonucleoside cyclic N-acylphosphoramidites with base-activated nucleosidic or nucleotidic 5'-hydroxyls proceeds via a single nucleophilic event. |
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MeSH term(s) | Models, Chemical ; Nuclear Magnetic Resonance, Biomolecular/methods ; Nucleic Acid Conformation ; Oligodeoxyribonucleotides/chemistry ; Organophosphorus Compounds/chemistry ; Phosphorus/chemistry |
Chemical Substances | Oligodeoxyribonucleotides ; Organophosphorus Compounds ; phosphoramidite ; Phosphorus (27YLU75U4W) |
Language | English |
Publishing date | 2002-02-20 |
Publishing country | United States |
Document type | Journal Article |
ZDB-ID | 3155-0 |
ISSN | 1520-5126 ; 0002-7863 |
ISSN (online) | 1520-5126 |
ISSN | 0002-7863 |
DOI | 10.1021/ja017190d |
Database | MEDical Literature Analysis and Retrieval System OnLINE |
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