Branched-chain aminodeoxy sugars. Methyl 3-C-aminomethyl-2-deoxy-α-D-ribo-hexopyranoside and methyl 3-C-aminomethyl-2-deoxy-α-D-arabino hexopyranoside

1970 ◽  
Vol 48 (19) ◽  
pp. 3034-3038 ◽  
Author(s):  
Alex Rosenthal ◽  
Khong-Seng Ong
Keyword(s):  
Catalytic Hydrogenation ◽  
Sodium Methoxide ◽  
Acetyl Derivative ◽  
Molar Equivalent ◽  
Branched Chain

Addition of methyl 4,6-O-benzylidene-2-deoxy-α-D-erythro-hexopyranosid-3-ulose (1) to excess nitromethane and 1 molar equivalent of sodium methoxide in methanol gave methyl 4,6-O-benzylidene-2-deoxy-3-C-nitromethyl-α-D-ribo-hexopyranoside (2) and the arabino stereoisomer 3 in 63 and 22% yields, respectively. The proof of structure of the branched-chain deoxy nitro sugars is described. Debenzylidenation of the nitro sugars afforded the partially blocked nitro sugars 4 and 5. Catalytic hydrogenation of the latter or of 2 and 3 yielded the branched-chain aminodeoxy sugars 7 and 9 (7 characterized as its N-acetyl derivative and 9 as its N-2,4-dinitrophenyl derivative).

New Route to Branched-chain Aminodeoxy Sugars by Reaction of Ketoses with Acetonitrile. Synthesis of Methyl 3-C-2′-Aminoethyl-2-deoxy-α-D-arabino-hexopyranoside

1974 ◽  
Vol 52 (1) ◽  
pp. 51-54 ◽  
Author(s):  
Alex Rosenthal ◽  
G. Schöllnhammer
Keyword(s):  
Catalytic Hydrogenation ◽  
Liquid Ammonia ◽  
High Yield ◽  
Lithium Amide ◽  
Branched Chain

Addition of methyl 4,6-O-benzylidene-2-deoxy-α-D-erythro-hexopyranosid-3-ulose (1) to acetonitrile in liquid ammonia at −50 to −60° in the presence of lithium amide gave, in high yield, crystalline methyl 4,6-O-benzylidene-3-C-cyanomethyl-2-deoxy-α-D-arabino-hexopyranoside (2) exclusively. The proof of structure 2 is described. Debenzylidenation of 2 afforded the branched-chain cyano glycoside 3. Compound 3 was converted into its 3,4,6-tri-O-acetate (8) and 4,6-di-O-p-nitrobenzoate (9) derivatives. Catalytic hydrogenation of 3 over rhodium on alumina yielded methyl 3-C-2′-aminoethyl-2-deoxy-α-D-arabino-hexopyranoside which was characterized as its N-2,4-dinitrophenyl derivative (7).

Synthetic use of the ribosyl derivatives of 2,4- and 2,5-thiazolidinediones

1979 ◽  
Vol 44 (5) ◽  
pp. 1475-1482 ◽  
Author(s):  
Hubert Hřebabecký ◽  
Zdeněk Točík ◽  
Jiří Beránek
Keyword(s):  
Hydrazine Hydrate ◽  
Hydrogen Chloride ◽  
Sodium Methoxide ◽  
Aqueous Ammonia ◽  
Hydroxylamine Hydrochloride ◽  
Acetyl Derivative ◽  
High Yield ◽  
Derivatives Of ◽  
Methanolic Ammonia

On ribosidation of 2,4-thiazolidinedione (2,5-thiazolidinedione, respectively), the 3-β-D-ribofuranosyl derivative is formed in high yield, either the benzoyl derivative Ia (IIa) or the acetyl derivative Ib (IIb). The unsubstituted ribosyl derivative Ic is formed from the acetyl derivative Ib by methanolic hydrogen chloride. The benzoylated ribosyl-2,4-thiazolidinedione Ia affords the benzoylated ribosylurea III on reaction with aqueous ammonia, the hydroxyethylurea derivative IVa with 2-aminoethanol, the semicarbazide derivative Va with hydrazine hydrate, the ribosylhydroxyurea derivative VIa on reaction with hydroxylamine hydrochloride and triethylamine, the benzoyl derivative of ribosylbiuret VII with O-methylisourea hydrochloride and triethylamine, and (analogously) ribosylisothiobiuret VIII with S-methylisothiourea. Methanolysis of the benzoyl derivative of hydroxyethylurea IVa with sodium methoxide affords the unprotected riboside IVb. Ribosylhydroxyurea VIb is formed on debenzoylation of compound VIa with methanolic ammonia. Acetylation of compound VIb furnishes the pentaacetyl derivative VIc.

Catalytic Hydrogenation of Phosphate Enol Esters Present in Branched Chain Dienepyranosides in a Route to Thromboxane Analogs from D-Galactose

1999 ◽  
Vol 18 (1) ◽  
pp. 15-29 ◽  
Author(s):  
Oscar Moradei ◽  
Cecile M. du Mortier ◽  
Alicia Fernández Cirelli ◽  
Joachim Thiem
Keyword(s):  
Catalytic Hydrogenation ◽  
Enol Esters ◽  
Branched Chain

Über 5-Hydroxymethyl-cytidin und 5-Hydroxymethyl-cytosin-N-3-β-D-glucopyranosid sowie über reaktionsfähige Vorstufen

1966 ◽  
Vol 21 (10) ◽  
pp. 942-952 ◽  
Author(s):  
Reinhard Brossmer ◽  
Erich Röhm
Keyword(s):  
Hydrochloric Acid ◽  
Benzyl Alcohol ◽  
Catalytic Hydrogenation ◽  
Sodium Methoxide ◽  
Room Temperature ◽  
Selective Removal ◽  
Protecting Groups ◽  
Hydroxymethyl Cytosine ◽  
Analogous Manner ◽  
Synthetic Intermediates

5-Benzyloxymethyl-NNH2-benzoyl-cytosine (4) is formed from 5-hydroxymethyl-cytosine (1) in 80% yield by benzylation and subsequent benzoylation. The benzylation readily takes place with benzyl alcohol and catalytic amounts of hydrochloric acid in tetrahydrothiophen-1.1-dioxide as solvent. — 4 is quantitatively converted in pyridine at room temperature to a toluene soluble mercury (II) salt 5.5 condenses easily with 2.3.5-tribenzoyl-D-ribofuranosyl chloride to give the β-nucleoside 6, no a-anomer being found. — The removal of all protecting groups by catalytic hydrogenation and treatment with sodium methoxide or ammonia leads to cristalline 5-hydroxymethyl cytidine 10 (ca. 60% yields based on 1). — In an analogous manner N-3-β-D-glucosyl-5-hydroxymethyl-cytosine 15 is prepared. — Selective removal of certain of the protecting groups in 6 and 11 yields potentially valuable synthetic intermediates.

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.

Oxidation of carbohydrates with chromium trioxide in acetic acid. I. Glycosides

1970 ◽  
Vol 23 (6) ◽  
pp. 1209 ◽  
Author(s):  
SJ Angyal ◽  
K James
Keyword(s):  
Acetic Acid ◽  
Hydrogen Atom ◽  
Catalytic Hydrogenation ◽  
Chromium Trioxide ◽  
Keto Ester ◽  
Keto Esters ◽  
Branched Chain ◽  
Acetyl Migration

Fully acetylated methyl β-D-hexopyranosides are oxidized by chromium trioxide in acetic acid to acetylated methyl 5-hexulosonates. Catalytic hydrogenation of these keto esters leads into the L-series. The corresponding a-D-glycosides are not oxidized in the same way, with the exception of methyl tetra-O-acetyl-α-D-idopyranoside. Both α- and β-anomers of the acetylated fnranosides are oxidized to aoetylated methyl 4-hexulosonates. The octaacetates of α- and β-lactose are similarly oxidized, the ring of the galactose moiety being opened. The methyl pyranoside of a branched-chain sugar, with no hydrogen atom on C5, is oxidized to a 4-keto ester, acetyl migration occurring from O4 to O5.

Branched-chain sugar nucleosides. II. 9-(3-Deoxy-3-C-hydroxymethyl-β-D-glucopyranosyl)-adenine

1969 ◽  
Vol 47 (17) ◽  
pp. 3263-3266 ◽  
Author(s):  
Alex Rosenthal ◽  
M. Sprinzl ◽  
H. J. Koch
Keyword(s):  
Sodium Methoxide ◽  
Branched Chain

Application of the oxo reaction to 1,2,4,6-tetra-O-acetyl-3-deoxy-α-D-erythro-hex-2-enopyranose (1), followed by acetylation of the oxo products, gave crystalline 1,2,3′,4,6-penta-O-acetyl-3-deoxy-3-C-(hydroxymethyl)-α-D-glucopyranose (2) in about 30% yield. Conversion of 2 into the branched-chain sugar bromide, followed by condensation of the latter with 6-benzamidochloromercuripurine afforded a blocked branched-chain sugar nucleoside (5) in 67% yield based on 2. The nucleoside (5) was deblocked with methanolic sodium methoxide to afford 9-(3-deoxy-3-C-hydroxymethyl-β-D-glucopyranosyl)-adenine (6) in 75% yield.

Synthesis of 6-chloro-9-(6′-deoxy-3′-C-methyl-2′,3′,4′-tri-O-methyl- β-D-allopyranosyl)purine: a branched-chain sugar nucleoside

1968 ◽  
Vol 46 (23) ◽  
pp. 3691-3694 ◽  
Author(s):  
G. B. Howarth ◽  
W. A. Szarek ◽  
J. K. N. Jones
Keyword(s):  
Acetyl Derivative ◽  
Purine Nucleoside ◽  
Fusion Method ◽  
Pyranose Ring ◽  
Branched Chain

The preparation of 6-deoxy-3-C-methyl-2,3,4-tri-O-metliyl-D-allopyranose (7), a branclied-chain sugar with the same constitution as nogalose from the antibiotic nogalamycin, is described. Condensation of the 1-O-acetyl derivative 8 with 6-chloropurine by the fusion method gave 6-chloro-9-(6′-deoxy-3′-C-methyl-2′,3′,4′-tri-O-methyl-β-D-allopyranosyl)purine (9), which to our knowledge is the first synthetic, purine nucleoside containing a branched-chain sugar with a pyranose ring.

Cyclizations of dialdehydes with nitromethane. XIV. The isolation of four crystalline methyl 3,6-dideoxy-3-nitro-α-L-hexopyranosides

1969 ◽  
Vol 47 (1) ◽  
pp. 99-103 ◽  
Author(s):  
Hans H. Baer ◽  
Karel Čapek
Keyword(s):  
Reaction Time ◽  
Catalytic Hydrogenation ◽  
Chromatographic Separation ◽  
Sodium Methoxide ◽  
Room Temperature ◽  
Total Yield

Cyclization of L′-methoxy-L-methyldiglycolic aldehyde (1) with nitromethane and sodium methoxide in methanol (40 min at room temperature) furnished four crystalline methyl 3,6-dideoxy-3-nitro-α-L-hexopyranosides in a combined yield of 75%. Chromatographic separation gave the gluco (2), manno (3), talo (4), and galacto (5) isomers in an approximate ratio of 18:8:3:1. Shortening of the reaction time to 25 min decreased the total yield to 53% at the expense of 2, the ratio of isolated products being 8:8:2.3:1.7. The configurations of the new nitro glycosides 3, 4, and 5 were proven by catalytic hydrogenation followed by N-acetylation, which gave the known 3-acetamido derivatives.

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