K. Araki et al., THE SYNTHESIS OF 2,3-DIDEOXY-2-FLUORO-3-C-METHYLPENTOSE-CONTAINING NUCLEOSIDES VIA [3,3]-SIGMATROPIC REARRANGEMENTS, Carbohydrate research, 249(1), 1993, pp. 139-161
[3,3]-Sigmatropic rearrangement of in situ-formed [0,0]-silyl ketene a
cetals of butenyl fluoroacetates was used as the key step in the synth
esis of racemic 2,3-dideoxy-2-fluoro-3-C-methylpentofuranoses. The pro
duct pentofuranoses were transformed further into pyrimidine and purin
e nucleosides. The conformations of the synthetic carbohydrates were c
onfirmed by single-crystal X-ray diffraction studies and indicated tha
t previous structural assignments made by NMR were in error.