Synthesis of Aldofuranosyl Nucleosides<sup>1</sup>

Kohn, Paul M.; Samaritano, Rita H.; Lerner, Léon M.

doi:10.1021/jo01343a044

Cited by 21 publications

(3 citation statements)

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“…Benzoylation of d - glycero - d - gulo -heptono-1,4-lactone ( 1 ) at room temperature for 2 h afforded the per- O -benzoyl- d - glycero - d - gulo -heptono-1,4-lactone ( 2 ) in good yield …”

Section: Resultsmentioning

confidence: 99%

A Carbohydrate Approach to the Enantioselective Synthesis of 1,3-Polyols

et al. 1996

J. Org. Chem.

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Treatment of per-O-benzoyl-D-glycero-D-gulo-heptono-1,4-lactone (2) with tertiary amines afforded selectively and with good yields the (5H)-furan-2-one derivatives 3, 4, and 5, formed by controlled elimination of one, two, or three molecules of benzoic acid, respectively. The stereochemistry for the exocyclic double bonds of 4 and 5 was determined by means of NMR techniques. Particularly, the furanone 4 was obtained from 2 ( approximately 90% yield) as a mixture of the E and Z diastereoisomers, which were separated by column chromatography or, more efficiently, by HPLC. The catalytic hydrogenation of compounds 4-E and 4-Z took place diastereoselectively, due to the chiral induction of the stereocenter located in the lateral chain. Thus, hydrogenation of 4-E led to a mixture of the 4,5-dihydro-(3H)-furan-2-ones having 3R,5S,2'S (D-xylo, 6) and 3S,5R,2'S (D-arabino, 7) configurations, with 6 as the major product; whereas the 4-Z isomer gave the same mixture, but being 7 preponderant. On hydrogenation of the original 4-E/Z mixture, compound 6 was obtained pure after recrystallization. O-Debenzoylation of 6gave 9, which was reduced with NaBH(4) to the 3,5-dideoxy-meso-xylo-heptitol (11). The peracetate (12) and perbenzoate (13) of the latter were prepared, and the 1-(tert-butyldiphenylsilyl)oxy derivative (16) was also synthesized via the 3'-(silyloxy)-4,5-dihydro-(3H)-furan-2-one 14. Chemoselective reduction of the lactone function of 6 with diisoamylborane gave the 2,5,6-tri-O-benzoyl-3,6-dideoxy-D-xylo-heptofuranose (17). The 3,5-dideoxy-D-arabino-heptitol (18), a diastereoisomer of 11, was also isolated and characterized.

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Section: Resultsmentioning

confidence: 99%

A Carbohydrate Approach to the Enantioselective Synthesis of 1,3-Polyols

et al. 1996

J. Org. Chem.

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“…(50) Similarly, a condensation of chloromercuri-N-benzoyladenine and 2,3:5,6-di-O-isopropylidine-D-gulofuranosyl chloride (43) gave, after acidic and basic deblocking, 9-p-n-gulofuranosyladenine(5l) (44). The structure was confirmed by comparison to material synthesized from tetra-O-benzoyl-n-gulofuranosyl chloride (52 ) where the trans rule dictated product stereochemistry, and by oxidation and then reduction, to 9-1X-L-lyxofuranosyladenine (45). This compound had the same properties, except for an equal and opposite rotation, as those obtained from the D-enantiopmorph.…”

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confidence: 85%

“…A condensation of the apparently unstable 4-acetamido-4-deoxy-2,3,5-tri-O-(p-nitrobenzoyl )-0-ribofuranosyl bromide with chloromercuri-6-benzamidopurine gave no product. However, the same purine was condensed with 4-acetamido-S-O-acetyl-2,3-di-Obenzoyl-4-deoxy-o-ribofuranosyl chloride or with the corresponding acetate (51) in the presence of TiCl 4 to yield a nucleoside that gave, after sodium methoxide deblocking, 9-( 4-acetamido-4-deoxy-p-o-ribofuranosyl)adenine (52) When the 3 position of the purine is substituted, glycosylation cannot occur at that position first. Glycosylation at this site was suggested, earlier in this section, to be the initial event in many purine glycosylations.…”

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confidence: 99%