The synthesis of 2,3-dideoxy-2-fluoro-3-C-methylpentose-containing nucleosides via [3,3]-sigmatropic rearrangements.
[3,3]-Sigmatropic rearrangement of in situ-formed [O,O]-silyl ketene acetals of butenyl fluoroacetates was used as the key step in the synthesis of racemic 2,3-dideoxy-2-fluoro-3-C-methylpentofuranoses. The product pentofuranoses were transformed further into pyrimidine and purine nucleosides. The conformations of the synthetic carbohydrates were confirmed by single-crystal X-ray diffraction studies and indicated that previous structural assignments made by NMR were in error.
Araki
K
K
Department of Chemistry, University at Albany, SUNY 12222.
Yun
W Q
WQ
O'Toole
J
J
Toscano
P J
PJ
Welch
J T
JT
D018360:Crystallography, X-Ray; D003854:Deoxyribonucleotides; D007202:Indicators and Reagents; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D008968:Molecular Conformation; D009705:Nucleosides / Q000138:chemical synthesis* / Q000737:chemistry*; D013329:Structure-Activity Relationship
D003854:Deoxyribonucleotides; D007202:Indicators and Reagents; D009705:Nucleosides