Issue 4, 1977

Crystal structure and molecular conformation of 2′,3′-O-methoxymethyleneuridine: X-ray and nuclear magnetic resonance investigation

Abstract

Crystals of the title compound are orthorhombic, space group P212121, with Z= 4 in a unit cell of dimensions: a= 16.48(1), b= 4.752(4), and c= 15.94(1)Å. The structure was determined from three-dimensional diffractometer data by direct methods, and refined by least-squares methods to R 4.04%. The dioxolan and ribofuranose rings are cis-connected about the C(2′)–C(3′) bond. The relatively flattened ribose ring (ϕmax. 23°) has the C(2′)-endo S-conformation, the glycosidic torsion angle lies in the normal anti range (χCN 56.5°) and the orientation of the C(5′)–O(5′) side-chain is gauchegauche. The crystal packing is governed by O(2)⋯ N(3)(2.896 Å) and O(4)⋯ O(5′)(2.907 Å) hydrogen bonds.

1 H n.m.r. spectroscopy reveals the existence of various conformational equilibria in solution. Vicinal coupling constants between ribose protons are consistent with an N [C(3′)-endo] S [C(2′)-endo] equilibrium with a slightly more puckered ribose ring than occurs in the crystal structure. The C(5′)–O(5′) side-chain shows almost equal populations of gauchegauche- and gauchetrans-rotamers with a minor contribution of the transgauche-conformation. The c.d. spectrum and the chemical shifts of the base protons H(5) and H(6) indicate a preference for the anti-conformation about the glycosidic bond.

Article information

Article type
Paper

J. Chem. Soc., Perkin Trans. 2, 1977, 487-493

Crystal structure and molecular conformation of 2′,3′-O-methoxymethyleneuridine: X-ray and nuclear magnetic resonance investigation

A. J. de Kok, C. Romers, H. P. M. de Leeuw, C. Altona and J. H. van Boom, J. Chem. Soc., Perkin Trans. 2, 1977, 487 DOI: 10.1039/P29770000487

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