Nucleosides. XIX. Structure of the 2'-Halogeno-2'-Deoxypyrimidine Nucleosides¹

Abstract

was taken to dryness in vacuo.To the residue was added a solution of 15 g. of sodium acetate in 200 ml. of water. After stirring for a few minutes a colorless amorphous solid was collected and washed with water. The yield was nearly quantitative. The solid was purified by precipitating from an ether solution with petroleum ether, m.p. 90-140°( efferv.), [a]24D +5°(c 0.2, acetone). Ultraviolet absorption properties in ethanol were Xmai 255, 229.5 ma; Xmin 246.5 nu>; ratio 260/230 me 0.63.

Nucleosides. XLIX. Nuclear magnetic resonance studies of 2′-and 3′-halogeno nucleosides. The conformations of 2′-deoxy-2′-fluorouridine and 3′-deoxy-3′-fluoro-β-D-arabinofuranosyluracil

“…The reluctance of 2,3-epoxides of sugars to react with this reagent was consistent with the experience of Taylor et al (30). Under less strenuous conditions, H F in dioxane had been found to give 2'-deoxy-2'-fluoro pyrimidine nucleosides in good yield from the appropriate 2,2'-anhydro derivatives (1). The fluoro nucleoside 3(F) was separated from other products of the reaction by partition chromatography on Celite (3 1).…”

The Reaction of O-Benzylidene Sugars with N-Bromosuccinimide.: VII. Stereochemical and Mechanistic Aspects in the Pyrimidine Nucleoside Series

“…As part of their extensive researches on the chemical modification of pyrimidine nucleosides, Fox and coworkers (3,4) have prepared several 2'-deoxy-2'-halogenouridines, by the 'For Part VI, see preceding paper, ref. the known 2'-bromo-2'-deoxyuridine 9 (3).…”

Mycobacterium tuberculosis Thymidine Monophosphate Kinase Inhibitors: Biological Evaluation and Conformational Analysis of 2′‐ and 3′‐Modified Thymidine Analogues

“…[16] Detritylation of 5 with 80 % HOAc quantitatively yielded nucleoside 6a [17] . Nucleophilic chlorination of 4 with 4  HCl in dioxane [18] resulted in the formation of 1-(3Ј-azido-2Ј-chloro-2Ј,3Ј-dideoxy-5-O-trityl-β--ribofuranosyl)-thymine (7a). Analogue 5 was treated with DAST [19] and, after detritylation, nicely afforded nucleoside 8a with the fluorine atom at the 2Ј-position of the sugar moiety in ribo (''DOWN'') configuration.…”

“…[22b][22c] Also, the 2Ј-α-fluoro atom in 8aϪb isosterically replaces a hydrogen atom and is known to greatly enhance the stability of the glycosidic bond. [18] Still, the affinity for 7aϪb and 8aϪb is moderate, i.e. Ͼ 100 µ.…”