Preparation of enantiomeric and racemic 2,3,4,5-tetrahydroxypentyl derivatives of adenine, cytosine and uracil

1982 ◽  
Vol 47 (10) ◽  
pp. 2786-2805 ◽  
Author(s):  
Antonín Holý
Keyword(s):  
Acid Hydrolysis ◽  
Sodium Borohydride ◽  
Catalytic Hydrogenation ◽  
Protecting Groups ◽  
Sodium Salts ◽  
Hydrolysis Of ◽  
Derivatives Of ◽  
Subsequent Acid

1-(Adenin-9-yl)-1-deoxy-DL-ribitol (III), -D-arabitol (IXa), -L-arabitol (XIVa), -DL-xylitol (XXIVa), 1-(cytosin-L-yl)-1-deoxy-D-arabitol (IXb), -L-arabitol (XIVb), 1-(uracil-1-yl)-1-deoxy-D-arabitol (IXc), -L-arabitol (XIVc) and -DL-xylitol (XXIVb) were prepared by reaction of 1-O-p-toluenesulfonyl-2,3:4,5-di-O-isopropylidenealditols Ib, VIIb, XIIb and XXIIb with sodium salts of adenine, N4-benzoylcytosine or 4-methoxy-2-pyrimidone followed by removal of the protecting groups. Condensation of the mentioned sodium salts with methyl 5-O-p-toluenesulfonyl-2,3-O-isopropylidene-β-D-ribofuranoside (IV) with subsequent acid hydrolysis and reduction with sodium borohydride afforded 1-(adenin-9-yl)-1-deoxy-L-ribitol (VIa) and 1-(cytosin-1-yl)-1-deoxy-L-ribitol (VIb). 1-(Adenin-9-yl)-1-deoxy-L-lyxitol (XVII), -L-lyxitol (XVIII) and -2-O-methyl-D-lyxitol (XXI) were prepared analogously. Acid hydrolysis of 5-(adenin-9-yl)-5-deoxy-4-O-benzyl-1,2-O-isopropylidene-α-D-xylofuranose (XXVa), followed by reduction with sodium borohydride and catalytic hydrogenation, gave 1-(adenin-9-yl)-1-deoxy-L-xylitol (XXVIb).

Synthesis of 4-deoxydaunosamine and 4-deoxyristosamine

1980 ◽  
Vol 58 (16) ◽  
pp. 1751-1758 ◽  
Author(s):  
Hans H. Baer ◽  
Hanna R. Hanna
Keyword(s):  
Acetic Acid ◽  
Acid Hydrolysis ◽  
Sodium Borohydride ◽  
Catalytic Hydrogenation ◽  
Sodium Acetate ◽  
Amino Glycoside ◽  
Hydrolysis Of

Treatment of methyl 3,6-dideoxy-2,4-di-O-methylsulfonyl-3-nitro-α-L-glucopyranoside (2) with sodium acetate and acetic acid in acetone gave methyl 4-O-acetyl-2,3,6-trideoxy-3-nitro-α-L-erythro-hex-2-enopyranoside (3) as a kinetic product, and the 2-O-acetyl-3,4,6-trideoxy-3-nitro-α-L-threo-hex-3-eno isomer 4 as the thermodynamically preferred product. Treatment of 2 or 4 with sodium borohydride produced a separable mixture of methyl 2,3,4,6-tetradeoxy-3-nitro-α-L-threo-hexopyranoside (5) and its α-L-erythro epimer (6), the latter being convertible into the former by base-catalyzed epimerization. Acid hydrolysis of 5 and 6 afforded the corresponding free nitro sugars 7 and 8. Catalytic hydrogenation of 5 led to the corresponding amino glycoside, isolated as the acetate 9 or hydrochloride 10; similarly, 6 gave the epimeric amine which was isolated as its acetate 14 or picrate 15. N-Trifluoroacetylation of 9 provided the N-trifluoroacetyl glycoside 12 which was hydrolyzed to give a 49% yield (overall from 2) of 2,3,4,6-tetradeoxy-3-trifluoroacetamido-L-threo-hexose (4-deoxy-N-trifluoroacetyldaunosamine, 13). Analogously, 14 afforded the epimeric N-trifluoroacetyl glycoside 17 which was hydrolyzed to give a 28% overall yield of 2,3,4,6-tetradeoxy-3-trifluoroacetamido-L-erythro-hexose (4-deoxy-N-trifluoroacetylristosamine, 18).

Branched-chain derivatives of acyclic adenosine analogs: Alkyl and hydroxymethyl derivatives of S-adenosyl-L-homocysteinase inhibitors substituted at the 2- and 3-position of the side chain

1989 ◽  
Vol 54 (1) ◽  
pp. 248-265
Author(s):  
Antonín Holý
Keyword(s):  
Acid Hydrolysis ◽  
Sodium Borohydride ◽  
Sodium Salt ◽  
Osmium Tetroxide ◽  
Sodium Perchlorate ◽  
Side Chain ◽  
Isopropylidene Derivative ◽  
Branched Chain ◽  
Hydrolysis Of ◽  
Derivatives Of

Reaction of 1,3-dichloro-2-propanone (VII) with methylmagnesium chloride, followed by alkaline hydrolysis, afforded 2-methylpropane-1,2,3-triol (VIII) which on treatment with 2,2-dimethoxypropane and subsequent tosylation gave 4-(p-toluenesulfonyloxymethyl)-2,2,4-trimethyl-1,3-dioxolane (IXb). Compound IXb was condensed with sodium salt of adenine and the intermediate X was acid-hydrolysed to give 9-(RS)-(2,3-dihydroxy-2-methylpropyl)adenine (XI). Oxidation of XI with sodium periodate led to 9-(2-oxopropyl)adenine (XII). 9-(RS)-(2-Hydroxy-2-hydroxymethyloctyl)adenine (XVI) was obtained analogously from compound VII and hexylmagnesium bromide via triol XIV. Methyl 2-bromomethyl-2-propenoate (XVII) reacted with sodium salt of adenine and the resulting methyl 2-(adenin-9-ylmethyl)-2-propenoate (XVIII) was hydroxylated with sodium perchlorate and osmium tetroxide. The obtained methyl (RS)-2-(adenin-9-ylmethyl)-2,3-dihydroxypropanoate (XIX) was alkali-hydrolysed to give sodium salt of the acid XX. Reduction of ester XIX with sodium borohydride furnished 9-(RS)-(2,3-dihydroxy-2-hydroxymethylpropyl)adenine (XXI). 1-Nonen-3-ol (XXIII), obtained by reaction of propenal with hexylmagnesium bromide, was converted by hydroxylation with osmium tetroxide into nonane-1,2,3-triol (XXIVa) and further into its 1-O-p-toluenesulfonate XXIVb which reacted with 2,2-dimethoxypropane to give 2,2-dimethyl-4-hexyl-5-(p-toluenesulfonyloxymethyl)-1,3-dioxolane (XXV). Compound XXV reacted with adenine and the resulting intermediate XXVI was converted into 9-(RS)-(2,3-dihydroxynonyl)adenine (XXVII) by acid hydrolysis. 9-(3-Methyl-2-buten-1-yl)adenine (XXVIII), obtained by alkylation of sodium salt of adenine with 1-bromo-3-methyl-2-butene, was oxidized with potassium permanganate in an acid medium to give 9-(3-hydroxy-2-oxo-3-methylbutyl)adenine (XXIX). This compound was converted into 9-(RS)-(2,3-dihydroxy-3-methylbutyl)adenine (XXX) by reduction with sodium borohydride. 4-C-Hydroxymethyl-1,2-O-isopropylidene-α-D-xylofuranose (XXXII) reacted with 2,2-dimethoxypropane under formation of 4-C-hydroxymethyl-1,2:3,5-di-O-isopropylidene derivative XXXIIIa whose p-toluenesulfonyl derivative XXXIIIb on treatment with adenine afforded 4-C-(adenin-9-yl)methyl-1,2:3,5-di-O-isopropylidene-α-D-xylofuranose (XXXIV). Acid hydrolysis of this compound, followed by oxidation in an alkaline medium, gave (2S,3R)-4-(adenin-9-yl)-3-hydroxymethyl-2,3-dihydroxybutanoic acid, isolated as its ethyl ester XXXVI.

Selective acid hydrolysis of 2,4,6-trimethylbenzyl esters and its application in peptide synthesis

1966 ◽  
Vol 19 (8) ◽  
pp. 1511 ◽  
Author(s):  
FHC Stewart
Keyword(s):  
Acid Hydrolysis ◽  
Peptide Synthesis ◽  
Trifluoroacetic Acid ◽  
Ester Group ◽  
Protecting Groups ◽  
Alkaline Conditions ◽  
Hydrolysis Of

Experiments with various N-acylamino acid 2,4,6-trimethylbenzyl esters have shown that the ester group is cleaved selectively by cold trifluoroacetic acid without affecting benzyloxycarbonyl, formyl, or phthaloyl amino-protecting groups present. The possible value of this selective behaviour in peptide syntheses where the use of alkaline conditions would be detrimental is illustrated by the synthesis of certain dipeptide derivatives.

scholarly journals A New Generation of Glycoconjugated Azo Dyes Based on Aminosugars

2015 ◽  
Vol 2015 ◽  
pp. 1-7
Author(s):  
Lorenzo Guazzelli ◽  
Giorgio Catelani ◽  
Felicia D’Andrea
Keyword(s):  
Acid Hydrolysis ◽  
Azo Dyes ◽  
Azo Dye ◽  
Protecting Groups ◽  
Third Generation ◽  
Sugar Moiety ◽  
The Third ◽  
New Generation ◽  
Monoazo Dyes ◽  
Hydrolysis Of

The third generation of glycoconjugated azo dyes (GADs) was prepared linking monoazo dyes to 6-amino-6-deoxy-d-galactose or 6′amino-6′-deoxylactose through mixed amido-ester connections. The complementary conjugation reactions were studied using the succinyl derivative of either the acetal protected aminosugar or the azo dye. Target “naturalized” GADs were obtained after acid hydrolysis of the acetal protecting groups present on the sugar moiety.

A Stereospecific Synthesis of L-Desosamine

1974 ◽  
Vol 52 (1) ◽  
pp. 122-124 ◽  
Author(s):  
Hans H. Baer ◽  
Chung-Wai Chiu
Keyword(s):  
Acid Hydrolysis ◽  
Nitro Group ◽  
Catalytic Hydrogenation ◽  
Glycosidic Bond ◽  
Stereospecific Synthesis ◽  
Borohydride Reduction ◽  
Amino Glycoside ◽  
Hydrolysis Of

L-Desosamine (3,4,6-trideoxy-3-dimethylamino-L-xylo-hexose), the enantiomer of a widely distributed antibiotics component, was synthesized by borohydride reduction of methyl 3,4,6-trideoxy-3-nitro-α-L-erythro-hex-3-enopyranoside followed by catalytic hydrogenation of the nitro group, N,N-dimethylation of the resulting saturated amino glycoside, and acid hydrolysis of the glycosidic bond.

1'-Derivatives of sucrose and their acid hydrolysis

1980 ◽  
Vol 33 (11) ◽  
pp. 2487 ◽  
Author(s):  
RD Guthrie ◽  
ID Jenkins ◽  
JJ Watters
Keyword(s):  
Acid Hydrolysis ◽  
Hydrolysis Of ◽  
Derivatives Of

Syntheses of 1'-chloro-1'-deoxy- and 1'-deoxy-sucrose are described. Several routes were investigated, the most successful being through 6,1',6'-tri-O-(2,4,6-trimethylbenzenesulfonyl)sucrose. Attempts to prepare 1'-deoxy-1'-fluorosucrose were unsuccessful. The rates of the acid-catalysed hydrolysis of 1'-chloro-1'-deoxysucrose and of 1'- deoxysucrose have been measured. These values are compared with that for sucrose itself. The mechanism of the hydrolyses is discussed.

ChemInform Abstract: KINETICS OF THE ACID HYDROLYSIS OF VINYL DERIVATIVES OF BENZIMIDAZOLE-2-THIONE, BENZOXAZOL-2-ONE AND -2-THIONE

1983 ◽  
Vol 14 (17) ◽  
Author(s):  
L. I. SVYATKINA ◽  
N. D. ABRAMOVA ◽  
L. L. DMITRIEVA ◽  
B. V. TRZHTSINSKAYA ◽  
G. G. SKVORTSOVA
Keyword(s):  
Acid Hydrolysis ◽  
Vinyl Derivatives ◽  
Kinetics Of ◽  
Hydrolysis Of ◽  
Derivatives Of

Acid hydrolysis of N-methyl derivatives of 4-phenyl-5-oxo-4,5-dehydroindeno[1,2-b]pyridine

1986 ◽  
Vol 22 (10) ◽  
pp. 1104-1107 ◽  
Author(s):  
V. K. Lusis ◽  
D. Kh. Mutsenietse ◽  
G. Ya. Dubur
Keyword(s):  
Acid Hydrolysis ◽  
Methyl Derivatives ◽  
Hydrolysis Of ◽  
Derivatives Of
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