1-(2,3-Dideoxy-erythro-beta-D-hexopyranosyl)cytosine: an example of the conformational and stacking properties of pyranosyl pyrimidine nucleosides. A crystallographic and computational approach.
C10H15N3O4, Mr = 241.25, orthorhombic, P2(1)2(1)2(1), a = 7.4013 (4), b = 8.7563 (5), c = 17.392 (1) A, V = 1127.1 (1) A3, Z = 4, Dm = 1.42, Dx = 1.422 Mg m-3, Ni-filtered Cu K alpha radiation, lambda = 1.54178 A, mu = 0.895 mm-1, F(000) = 512, T = 293 K, final R = 0.044 for 1024 unique observed [F greater than or equal to 6 sigma (F)] reflections. The conformational parameters are in accordance with the IUPAC-IUB Joint Commission on Biochemical Nomenclature [Pure Appl. Chem. (1983), 55, 1273-1280] guidelines. In order to assess the possible use of pyranosyl-modified pyrimidine nucleosides in the design of new synthetic oligonucleotides, the conformational and packing properties of 13 structures were examined. From this study, it becomes clear that the pyrimidine-base geometry is independent of the sugar ring type (furanosyl- or pyranosyl-like). The bases are always positioned in an equatorial orientation on the pyranoside sugar, which means that the sugar adopts a 4C1 conformation in alpha- and 4C1 in beta-enantiomers. As a result of the anomeric effect the O5'-C1' bond length is 0.020 (4) A shorter than the C5'-O5' distance (C1' is the anomeric C atom). The O5'-C1'-N1-C2 torsion angle chi in the 13 nucleosides is centered around 244 (8) degrees and varies from 196.4 (3) to 287.0 (2) degrees. Molecular-mechanics calculations on uncharged pyranosyl nucleosides are found to be less accurate compared with semi-empirical quantum-chemical methods or molecular-mechanics calculations on charged molecules.(ABSTRACT TRUNCATED AT 250 WORDS)
De Winter
H L
HL
Laboratorium voor Analytische Chemie en Medicinale Fysicochemie, Instituut voor Farmaceutische Wetenschappen, Katholieke Universiteit Leuven, Belgium.
De Ranter
C J
CJ
Blaton
N M
NM
Peeters
O M
OM
Van Aerschot
A
A
Herdewijn
P
P
D003461:Crystallography; D009690:Nucleic Acid Conformation; D011741:Pyrimidine Nucleosides / Q000737:chemistry*; D014961:X-Ray Diffraction; D016047:Zalcitabine / Q000031:analogs & derivatives* / Q000737:chemistry
C075502:1-(2,3-dideoxy-hexopyranosyl)cytosine; D011741:Pyrimidine Nucleosides; D016047:Zalcitabine