Branched-chain sugar nucleosides. III. 9-(3-Deoxy-3-C-methyl-β-D-allofuranosyl and ribofuranosyl)adenine

1969 ◽  
Vol 47 (21) ◽  
pp. 3941-3946 ◽  
Author(s):  
Alex Rosenthal ◽  
Matej Sprinzl
Keyword(s):  
Sodium Borohydride ◽  
Titanium Tetrachloride ◽  
Borohydride Reduction ◽  
Reaction Conditions ◽  
Sodium Metaperiodate ◽  
Sodium Borohydride Reduction ◽  
Branched Chain ◽  
Wittig Reagent

Condensation of triphenylphosphinemethylene (Wittig reagent) with 5-O-benzyl-1,2-O-isopropyl-idene-α-D-erythro-pentafuranos-3-ulose and with 1,2:5,6-di-O-isopropylidene-α-D-ribo-hexofuranos-3-ulose (1) afforded 5-O-benzyl-1,2-O-isopropylidene-3-deoxy-3-C-methylene-α-D-ribofuranose in 36% yield and 1,2:5,6-di-O-isopropylidene-3-C-methylene-α-D-ribo-hexofuranose (2) in 55% yield, respectively. A detailed study of the affect of reaction conditions on the yield of the unsaturated sugar is described. Hydrogenation of 2 proceeded stereoselectively to yield 4 which was hydrolyzed selectively to the 1,2-O-monoisopropylidene derivative 5. Benzoylation of the latter gave 6 which was converted by acetolysis to the 1,2-diacetate 7. Condensation of this compound with 6-benzamidochloromercuripurine in the presence of titanium tetrachloride followed by deblocking with methanolic sodium meth-oxide, yielded 9-(3-deoxy-3-C-methyl-β-D-allofuranosyl)adenine (10) in 48% yield based on 7. Sodium metaperiodate oxidation of 10, followed by sodium borohydride reduction of the aldehydo derivative, afforded 9-(3-deoxy-3-C-methyl-β-D-ribofuranosyl)adenine (11) in 85% yield.

Branched-chain sugar nucleosides. IV. 9-(3-Deoxy-3-C-"hydroxymethyl"-β(and α)-D-allofuranosyl and ribofuranosyl)adenine

1969 ◽  
Vol 47 (23) ◽  
pp. 4477-4481 ◽  
Author(s):  
Alex Rosenthal ◽  
Matej Sprinzl
Keyword(s):  
Hydrogen Peroxide ◽  
Sodium Methoxide ◽  
Titanium Tetrachloride ◽  
Total Yield ◽  
Borohydride Reduction ◽  
Peroxide Oxidation ◽  
Alkaline Hydrogen Peroxide ◽  
Sodium Metaperiodate ◽  
Sodium Borohydride Reduction ◽  
Branched Chain

Hydroboration followed by alkaline hydrogen peroxide oxidation of 1,2:5,6-di-O-isopropylidene-3-C-methylene-α-D-ribo-hexofuranose (2) yielded 3-deoxy-3-C-"hydroxymethyl"-1,2:5,6-di-O-isopropylidene-α-D-allofuranose (3) and partially hydrolyzed 3 in a total yield of 88%. Compound 3 was hydrolyzed selectively to the 1,2-monoisopropylidene derivative 5, which was converted via benzoylation followed by acetolysis into the 1,2-diacetate 7. Condensation of the latter compound with chloromercuri-N-benzoyladenine in the presence of titanium tetrachloride, followed by deblocking with methanolic sodium methoxide, yielded 9-(3-deoxy-3-C-"hydroxymethyl"-β(and α)-D-allofuranosyl)adenine in yields of 44 and 4% respectively, based on 7. The over-all yield of 10 based on 3 is 20%. Sodium metaperiodate oxidation of 10, followed by sodium borohydride reduction of the aldehydo-derivative, afforded 9-(3-deoxy-3-C-"hydroxymethyl"-β-D-ribofuranosyl)adenine (11) in 81% yield.Direct acetolysis of 3, followed by conversion of the mixture of peracetates into a mixture of glycosyl chlorides, and finally condensation of the latter with 8 gave the blocked crystalline β-D-nucleoside 9 in an over-all yield of about 9%, based on 3. Subsequent unblocking of 9 gave a nucleoside having the same physical constants as 10.

THE ALKALOIDS OF LYCOPODIUM ANNOTINUM: PART V. THE STRUCTURE AND STEREOCHEMISTRY OF LYCOFOLINE

1962 ◽  
Vol 40 (2) ◽  
pp. 236-239 ◽  
Author(s):  
F. A. L. Anet ◽  
M. Ahmad ◽  
N. H. Khan
Keyword(s):  
Sodium Hydroxide ◽  
Sodium Borohydride ◽  
Borohydride Reduction ◽  
Reaction Conditions ◽  
Lycopodium Annotinum ◽  
Sodium Borohydride Reduction

Lycofoline forms a monoacetyl or a diacetyl derivative, depending on the reaction conditions. Hydrogenation of lycofoline yields dihydrolycofoline. Sodium borohydride reduction of acrifoline under non-epimerizing conditions gives the known acrifolinol, but reduction in the presence of sodium hydroxide gives both acrifolinol and lycofoline. From these reactions as well as the evidence of n.m.r. spectra, lycofoline is shown to have structure IV.

Synthesis and spectroscopic investigations of 1,4-benzothiazepine derivatives

1987 ◽  
Vol 65 (1) ◽  
pp. 175-181 ◽  
Author(s):  
János Szabó ◽  
Gábor Bernáth ◽  
Ágnes Katócs ◽  
Lajos Fodor ◽  
Pál Sohár
Keyword(s):  
Nmr Spectroscopy ◽  
Sodium Borohydride ◽  
Ring Closure ◽  
Similar Reaction ◽  
Borohydride Reduction ◽  
Phosphoryl Chloride ◽  
Reaction Conditions ◽  
Phenyl Sulfide ◽  
Sodium Borohydride Reduction ◽  
Acyl Derivatives

The reaction of sodium 3,4-dimethoxythiophenolate (1) with 2-bromoethylamine (2) gave 2′-aminoethyl-3,4-dimethoxy-phenyl sulfide hydrochloride (3). Ring closure of the acyl derivatives 4a–c with phosphoryl chloride furnished the 2,3-dihydro-1,4-benzothiazepines 5a–c. In a reaction competing with the cyclization, the acid amides 4 decomposed to 2′-chloroethyl-3,4-dimethoxyphenyl sulfide (7) and the corresponding nitrile. A few derivatives (8–10) of 5c were prepared. Sodium borohydride reduction of 5b, c yielded the 2,3,4,5-tetrahydro-1,3-benzothiazepines 11a, b. With substituted acetyl chlorides, compounds 5c and 10 were converted to the β-lactam derivatives 12a–f and 13, the configurations and conformations of which were determined by nmr spectroscopy; under similar reaction conditions the analogous compounds 5a, b gave the enamides 14, 15, and 16.

1,2-Benzothiazines. II. The Preparation and Sodium Borohydride Reduction of 3-Acyl-2H-1,2-benzothiazin-4(3H)-one 1,1-Dioxides1

1965 ◽  
Vol 30 (7) ◽  
pp. 2241-2246 ◽  
Author(s):  
Harold Zinnes ◽  
Roger A. Comes ◽  
Francis R. Zuleski ◽  
Albert N. Caro ◽  
John Shavel
Keyword(s):  
Sodium Borohydride ◽  
Borohydride Reduction ◽  
Sodium Borohydride Reduction
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