Glucofuranose 1,2-0-isopropylidene-6-thio

With the other types of neutral dithiocarbonate (X—S—CO—SR and X—S—CS—OR), where the carbohydrate residue is esterified through sulfur instead of oxygen, alkaline hydrolysis yields the salt of a thiol (X— SH). In the cases of 1,2 5,6-di-0-isopropylidene-3-/S -[(methylthio)thio-carbonyl]-3-thio-D-glucofuranose (LXVI) and 2,3,4,6-tetra-0-acetyl-l-(S-(ethoxythiocarbonyl)-l-thio-/9-D-glucopyranose (LXXXI) this change was brought about very readily with methanolic ammonia, being accompanied in the latter instance by deacetylation. Sodium and potassiiun alkoxides have also been used. ... 

The acetolysis of 3,6-di-0-acetyl-5-(S-acetyl-l,2-0-isopropylidene-5-thio-D-glucofuranose (352) afforded the pyranose thio sugar (353), and... 

The first synthesis of a thio sugar by epoxide scission to be reported was the preparation of 1,2-0-isopropylidene-6-thio-D-glucose (67, R = H) from 5,6-anhydro-l,2-0-isopropylidene-a-D-glucofuranose (66) by the action of hydrogen sulfide. The product was isolated as the crystalUne... 

Scheme 4 shows a novel route to 2-thiosophorose (51) which equilibrates readily with 2-thioepisophorose (52). Preparation of diheterodisaccharide 53 and related glycosidase inhibitors involved opening of bis-aziridine 54 with l,2 5,6-di-0-isopropylidene-3-thio-a-D-glucofuranose. ... 

Small pieces of Na added to a soln. of 6-0-acetyl-5-S-acetyl-3-0-benzyl-l,2-0-isopropylidene-5-thio-a-D-glucofuranose in liq. NH3 and dry 1,2-dim ethoxy ethane until the blue color persists for 15 min. or more crude l,2-0-isopropylidene-5-thio-a-D-glucofuranose. Y almost 100%. Also from 5-S-acetyl-3,6-di-0-benzyl-l,2-0-isopropylidene-5-thio-a-D-glucofuranose s. U. G. Nayak and R. L. Whistler, J. Org. Chem. 34, 97 (1969). 

An ale. soln. of 275 mg. 6-deoxy-l,2-0-isopropylidene-3-0-methyl-6-thio-a-D-glucofuranose 5,6-dithiocarbamate treated 5 min. with 12.5 M NaOH-soln. -> 210 mg. 5,6-dideoxy-5,6-epithio-l,2-0-isopropylidene-3-0-methyl-/ -L-idofura-nose. F. reactions s. B. S. Shasha and W. M. Doane, Carbohyd. Res. 34, 370 (1974). 

The oxidation at sulphur of 6-5-benzyl-l,2-0-isopropylidene-3-0-methyl-6-thio-a-D-glucofuranose by w-chloroperbenzoic acid has been studied. 

O-Isopropylidene 1,2-O-Isopropyli-dene-6-thio-a-D-glucofuranose CsHisOjS 236.288 Mp 96-97°. Md -14 (CHCI3). 

Acetamido-3-deoxy-l,2 5,6-di-0-isopropylidene-P-L-idofuranose, A-292 3-Acetamido-3-deoxy-P-D-galactopyranose, A-207 3-Acetamido-3-deoxy-P-D-glucopyranose, A-267 3-Acetamido-3-deoxy-1,2-0 -isopropylidene-a-D-allofuranose, A-157 3-Acetamido-3-deoxy-l,2-0-isopropylidene-a-D-glucofuranose, A-267 3-Acetamido-3-deoxy-l,2-0-isopropylidene-a-D-gulofuranose, A-280 3-Acetamido-3-deoxy-l,2-0-isopropylidene-P-L-lyxofuranose, A-297 3-Acetamido-3-deoxy-5-thio-D-xylose, A-352... 

Diisopropylidene-5-thio-a-D-allofuranose, T-54 1,2 5,6-Di-0 -isopropylidene-3-thio-a-D-glucofuranose, T-72... 

Dideoxy-6-phosphono-D-ara6/ o-hexose (25), an isosteric analogue of D-arabinose 5-phosphate, has been synthesized. " l,2-0-Isopropylidene-6-thio-a-D-glucofuranose reacted with phosphorus trichloride-triethylamine in absolute ether to give the 3,5,6-bicyclothiophosphite (26). ... 

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