Branched-chain 2-deoxy sugars. V. Application of the Wittig reaction to methyl 3,4-O-isopropylidene-β-D-erythro-pentopyranosid-2-ulose and attempted synthesis of nucleosides of 2-deoxy-2-C-methylpentoses

1970 ◽  
Vol 48 (20) ◽  
pp. 3253-3257 ◽  
Author(s):  
Alex Rosenthal ◽  
Matej Sprinzl
Keyword(s):  
Hydrogen Chloride ◽  
Wittig Reaction ◽  
Yield Reduction ◽  
Ruthenium Tetroxide ◽  
Branched Chain ◽  
Deoxy Sugars

Oxidation of methyl 3,4-O-isopropylidene-β-D-arabinopyranoside (1) with ruthenium tetroxide afforded methyl 3,4-O-isopropylidene-β-D-erythro-pentopyranosid-2-ulose (2) in 78% yield. Condensation of methylenetriphenylphosphorane with 2 in the presence of H-butyllithium yielded methyl 3,4-O-isopropylidene-2-deoxy-2-C-methylene-β-D-erytho-pentopyranoside (3) in 55% yield. Reduction of the latter with 10% palladium-on-charcoal gave a 7:1 mixture of two isomeric 2-deoxy-2-C-methylpentoside derivatives in 95% yield: the preponderant product had the D-ribo configuration. The fully blocked methyl glycosides were de-isopropylidenated with methanolic hydrogen chloride to yield 6 and 7 and these were converted into the p-toluoyl esters (8) and (9). Attempts to utilize the latter in the synthesis of nucleosides of 2-deoxy-2-C-methyl pentoses were unsuccessful.

scholarly journals Synthesis of olivomycose (2,6-dideoxy-3-C-methyl-L-arabino-hexose)

1969 ◽  
Vol 47 (23) ◽  
pp. 4467-4471 ◽  
Author(s):  
E. H. Williams ◽  
W. A. Szarek ◽  
J. K. N. Jones
Keyword(s):  
Wittig Reaction ◽  
High Yield ◽  
Lithium Aluminium Hydride ◽  
Ruthenium Tetroxide ◽  
Lithium Aluminium ◽  
Acid Catalyzed ◽  
Hydrolysis Of

Oxidation of methyl 4,6–O-benzylidene-2-deoxy-α-L-arabino-hexopyranoside (1) with ruthenium tetroxide gave the 3-ketone 2 in high yield. A Wittig reaction between methylenetriphenylphosphorane and compound 2 gave methyl 4,6-O-benzylidene-2,3-dideoxy-3-C-methylene-α-L-erythro-hexopyranoside (3), which was hydrated by the oxymercuration–demercuration procedure to afford methyl 4,6-O-benzylidene-2-deoxy-3-C-methyl-α-L-arabino-hexopyranoside (4). The reaction of compound 4 with N-bromosuccinimide gave methyl 4-O-benzoyl-6-bromo-2,6-dideoxy-3-C-methyl-α-L-arabino-hexopyranoside (5) in high yield. Treatment of compound 5 with lithium aluminium hydride followed by acid-catalyzed hydrolysis of the resultant product, gave L-olivomycose (6).

Addition of pseudohalogens to unsaturated carbohydrates. III. Synthesis of 3-deoxy-3-C-nitromethyl-D-allose, a branched-chain nitro sugar

1969 ◽  
Vol 47 (23) ◽  
pp. 4473-4476 ◽  
Author(s):  
W. A. Szarek ◽  
J. S. Jewell ◽  
I. Szczerek ◽  
J. K. N. Jones
Keyword(s):  
Sodium Borohydride ◽  
Wittig Reaction ◽  
Furanose Form ◽  
Acid Catalyzed ◽  
Branched Chain ◽  
Hydrolysis Of

Addition of nitryl iodide to 3-deoxy-1,2:5,6-di-O-isopropylidene-3-methylene-α-D-ribo-hexofuranose (2), followed by treatment of the product with sodium borohydride, gave crystalline 3-deoxy-1,2:5,6-di-O-isopropylidene-3-C-nitromethyl-α-D-allofuranose (3); the branched-chain unsaturated sugar (2) was prepared by way of a Wittig reaction with 1,2:5,6-di-O-isopropylidene-α-D-ribo-hexofuranos-3-ulose (1). Acid-catalyzed hydrolysis of 3 afforded 3-deoxy-3-C-nitromethyl-D-allose, which exists predominantly in the β-D-furanose form (4).

PREPARATION OF SOME NEW BRANCHED-CHAIN CARBOHYDRATES FROM D-α-FRUCTOHEPTONIC LACTONE

1954 ◽  
Vol 32 (4) ◽  
pp. 404-414 ◽  
Author(s):  
R. J. Woods ◽  
A. C. Neish
Keyword(s):  
Nitric Acid ◽  
Hydrochloric Acid ◽  
Hydrogen Chloride ◽  
Sodium Borohydride ◽  
Periodic Acid ◽  
Equimolar Amount ◽  
Glassy Material ◽  
Sodium Amalgam ◽  
Aldonic Acid ◽  
Branched Chain

D-α-Fructoheptonic lactone (I) was oxidized with an equimolar amount of periodic acid to give formaldehyde and a hexuronic lactone (II) which was hydrolyzed to crystalline 4-C-hydroxymethyl-L-xyluronic acid (III), (68% yield). Hydrogenation of III gave an aldonic acid which was isolated as crystalline 2-C-hydroxymethyl-L-xylonic lactone (V). Reduction of V by sodium amalgam gave 2-C-hydroxymethyl-D-xylose (VI), which crystallized after purification as the 2,5-dichlorophenylhydrazone. Hydrogenation of VI gave 1,1-di(C-hydroxymethyl)-D-threitol (VII) which was purified as the crystalline hexaacetate. Treatment of III with methanolic hydrogen chloride gave a glassy material which was reduced by sodium borohydride and hydrolyzed by hydrochloric acid to give 4,4-di(C-hydroxymethyl)-D-threose (IX), which was isolated and characterized as the crystalline 2,5-dichlorophenylhydrazone. Oxidation of III by either bromine or nitric acid gave 2-C-hydroxymethyl-D-xylaric acid (IV), which was characterized as the crystalline ammonium salt.

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