Sur la stéréospécificité de la ribonucléoside-diphosphate-réductase: préparation de désoxyribonucléosides pyrimidiques deutérés

Methyl 2-deoxy-3,5,6-tri-O-p-nitrobenzoyl- -ribo-hexofuranoside was converted into the glycosyl halide which was then condensed with 2,4-bis(trimethylsilyloxy)-pyrimidine in the presence of mercuric chloride to give, after alkaline methanolysis, 1-(2-deoxy-β- -ribo-hexofuranosyl)uracil, in a yield too low for the reaction to be applied to deuterated compounds. Methyl 2-deoxy- -allofuranoside-2-d was degraded into methyl 2-deoxy- -arabinofuranoside-2-d. Its di-p-nitrobenzoate was converted into the glycosyl halide which was coupled with 2,4-bis(trimethylsilyloxy)-pyrimidine to give, after alkaline hydrolysis, deuterated deoxyuridine. Thiationammonolysis of a mixture of the 3′,5′-di-p-nitrobenzoates of the latter compound and its anomer gave the corresponding deoxycytidines. Comparison of the n.m.r. spectra of these compounds to that of deuterated deoxycytidine, prepared by the enzymic reduction of cytidine 5′-pyrophosphate with the Escherichia coli system in the presence of deuterium oxide confirmed that the substitution of a hydroxyl group by a hydrogen atom proceeds with retention of configuration.