Tricyclic nucleosides derived from D-glucose: Synthesis and conformational behaviour

Two anomeric nucleosides with tricyclic carbohydrate moieties, 3 and 14, are synthesised in 11 steps from diacetone-D-glucose, taking advantage of a stereoselective Grignard reaction, a stereoselective dihydroxylation and a regioselective tandem ring-closing procedure. The configuration of 3 is confirmed by measuring the 3JHH coupling constants in connection with molecular modelling and ab initio calculations, as these exclude alternative tricyclic nucleoside structures. The conformational preference for 3 is described. The furanose ring is found to be in an O-4′-endo conformation and the γ torsion angle in the +ap range.

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