Preparation from D-glucose

Deoxy-D-jcylo hexose 6-(dihydrogen phosphate) (21) has also been synthesized (2) the reaction sequence makes use of 3-deoxy l 2,5 6-di-O-isopropylidene D-galactofuranose (16), a compound that can be easily prepared from D-glucose (2, 60). The mono-isopropylidene derivative (17) formed by partial hydrolysis of the di-ketal is converted into the 6-tosylate (18) by reaction with one molar equivalent of p-toluenesulfonyl chloride. From this the epoxide (19) is formed by reaction with sodium methoxide. Treatment of the anhydro sugar with an aqueous solution of disodium hydrogen phosphate (26) leads to the 6-phosphate (20)... 

The reaction of the aldehyde 174, prepared from D-glucose diethyl dithio-acetal by way of compounds 172 and 173, with lithium dimethyl methyl-phosphonate gave the adduct 175. Conversion of 175 into compound 176, followed by oxidation with dimethyl sulfoxide-oxalyl chloride, provided diketone 177. Cyclization of 177 with ethyldiisopropylamine gave the enone 178, which furnished compounds 179 and 180 on sodium borohydride reduction. 0-Desilylation, catalytic hydrogenation, 0-debenzyIation, and acetylation converted 179 into the pentaacetate 93 and 5a-carba-a-L-ido-pyranose pentaacetate (181). 

D-Glucosone (XII), prepared from D-glucose phenylosazone (XI) by the action of concentrated hydrochloric acid, is treated in aqueous solution with potassium cyanide. The imino-D-glucoascorbic acid (XIV) which readily separates shows many of the properties of ascorbic acid. Thus it shows a strong selective absorption band in the ultra-... 

Bayne, Fewster and Mitchell16 prepared VII by the method of Stacey and Turton, and recorded physical properties closely agreeing with those reported by Maurer.66 The compound was clearly related to D-glucosone, prepared from D-glucose phenylosazone and by direct oxidation, since, on treatment with dry acetone containing concentrated sulfuric acid, it gave crystalline tri-0-isopropylidene-(2-hydroxy-D-arabmo-hexose). 7... 

Reactions of a 2-benzazepin-l-one derivative involving a spiroannelation procedure from 76 to afford the spiro-cyclic 3-benzazepine derivative 83 via 77-82 have been reported (Scheme 9) <2005H(65)1359>, while other chiral substituted 2-benzazepines have been prepared from D-glucose via furo[3,2-f][2]benzazepine derivatives <2005S2307>. 

Boron trifluoride etherate-mediated cyclization (Equation 24) of the pyran derivative 62 (prepared from D-glucose) is used in the synthesis of AB ring system of ciguatoxine <1997T3057>. 

D-Erythroascorbic acid (D-g/vccro-2-pentenono-1,4-lactone, 142), was prepared from D-glucose by degradative oxidation to potassium D-arabinonate, which was acidified and lactonized. The lactone 143 was converted in one step into the 2-keto methyl ester 144, which finally was tautomerized in hot methanolic sodium acetate, affording D-erythroascorbic acid (142) as a crystalline solid.328... 

The inexpensive, commercially available D-g/ycero-D-gw/o-heptono-1,4-lactone ( glucoheptonolactone since it is prepared from D-glucose) is the precursor for the 2,7-dibromo-2,7-dideoxy-D-g/ycm -D-/afo-heptono-1,4-lactone (1) (Scheme 13) which, via the unsaturated lactone 2a and radical induced carbocyclisation, could be transformed into the crystalline dihydroxy cyclopentane lactone 4a in high yield (Scheme 14). This short and efficient synthesis of the cis-fused cyclopentane lactone provides easy access to a chiral synthon which might be modified stereospecifically for many purposes. Such... 

Ziegler149 has reported a highly efficient synthesis of the very similar M. avium serovar 21 trisaccharide hapten with attached linker-arm (89). The blockwise construction minimizes the manipulation of protecting groups and hence the number of steps in the overall synthesis. The synthesis featured two key operations (1) the kinetically controlled diastereoselective preparation from D-glucose of the... 

A total synthesis of 5-ep/-trehazolin (trehalostatin, 3) was accomplished starting with D-glucose (Scheme 13).71 Thus, benzylation of the allyl alcohol 83, prepared from d-glucose in 10 steps,70 gave 95, and cleavage of the silyl group afforded 96. Sharpless epoxidation of 96 by l-DIPT or d-DIPT furnished the two stereoisomers of 97 and 98. Benzylation of the epoxide 98 afforded 99, which upon azidolysis afforded the... 

Epoxide cleavage, Sodium selenophenolate reacts with the furanose 1, prepared from D-glucose, to form the diselenide 3 in quantitative yield. This reaction involves formation and cleavage of the epoxide 2, which can be also prepared by treatment of 1 with NaH. The epoxide is cleaved regiospecifically by attack from the less hindered side at C4. The phenylseleno group can be removed reductively by Raney nickel. The product was used to prepare isoepiallomuscarine (5). 

A second fragment, also derived from D-glucose, which will correspond to C-13 to C-16, was constructed as follows. Deoxyxylose 11 (prepared from D-glucose by literature procedures) was oxidatively cleaved, reduced, and tosylated to give compound 12. Displacement with Nal and conversion to the phosphonium salt gave 13 in good overall yield. 

A series of novel 3 -thiacarbocyclic nucleosides 240, carrying purine and pyrimidine bases, have been prepared from D-glucose. The key steps were the treatment of dimesylate 237 with Na2S, inversion at C-4 by the Mitsunobu reaction (BzOH, PhsP, and DEAD), and coupling of mesylate 239 with the nucleoside base in the presence of potassium carbonate, followed by deprotection. None of these nucleoside were active against HIV-1. 

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