Arabinitol , acetyl derivatives

Mannitol hexanitrate is obtained by nitration of mannitol with mixed nitric and sulfuric acids. Similarly, nitration of sorbitol using mixed acid produces the hexanitrate when the reaction is conducted at 0—3°C and at —10 to —75°C, the main product is sorbitol pentanitrate (117). Xylitol, ribitol, and L-arabinitol are converted to the pentanitrates by fuming nitric acid and acetic anhydride (118). Phosphate esters of sugar alcohols are obtained by the action of phosphorus oxychloride (119) and by alcoholysis of organic phosphates (120). The 1,6-dibenzene sulfonate of D-mannitol is obtained by the action of benzene sulfonyl chloride in pyridine at 0°C (121). To obtain 1,6-dimethanesulfonyl-D-mannitol free from anhydrides and other by-products, after similar sulfonation with methane sulfonyl chloride and pyridine the remaining hydroxyl groups are acetylated with acetic anhydride and the insoluble acetyl derivative is separated, followed by deacetylation with hydrogen chloride in methanol (122). Alkyl sulfate esters of polyhydric alcohols result from the action of sulfur trioxide—trialkyl phosphates as in the reaction of sorbitol at 34—40°C with sulfur trioxide—triethyl phosphate to form sorbitol hexa(ethylsulfate) (123). 

In our laboratory we routinely use columns (3 m x 2.2 mm) containing 3% w/w OV-225 at 200°C to obtain baseline resolution of the acetylated derivatives of rhamnitol, arabinitol, xylitol, mannitol, galacti-tol, and glucitol in approximately 45 min (Selvendran et al., 1979). With high quality columns containing OV-225, it may also be possible to achieve partial resolution of the acetylated derivatives of rhamnitol and fucitol. 

An amidrazone (58) derived from 5-amino-5-deoxy-L-fuconolactam was found to inhibit a recombinant human a-L-fucosidase with a K -value of 820 nmol/1 [ 111 ]. A simple synthesis of 1,5-dideoxy-1,5-imino-D-arabinitol (59), previously prepared by Ganem et al. [49] as a potential maimosidase inhibitor, was applied to the affinity purification of a-L-fucosidase from bovine kidney by an improved method and the characterization of the enzyme thus obtained [112]. The relatively low affinity of this compound to the enzyme (Kj 2.2 pmol/1 at pH 7) compared to 1-deoxyfuconoJirimycin (51) turned out to be advantageous in terms of enzyme recovery and yield. Structurally related, suitably protected 5-amino-5-deoxy-D-arabinopyranose (60), was coupled with a N-acetyl-6-deoxy-6-thio-D-glucosaminide (61) to give a stable thioglycoside (62) [113]. 

From such a reaction scheme, it would, however, be expected that a derivative (44) of 2,5-anhydro-D-arabinitol would be obtained from 3,4-di-0-acetyl-l,5-anhydro-2-deoxy-D-erythro-pent-l-enitol (39a), and not the ribo product observed. 

Cyclitols, Alditols, and otho Acyclic Derivatives.—epi-Inositol.SrClj/ dl-mannitol, ° l,3,4,6-tetra-0-acetyl-2,5-0-methylene-D-mannitol/ o-mannitol l,2 3,4 5,6-tris(phenylboronate)/ l-(l-S-ethyl-l-thio-D-arabinitol-l-yl)-5-fluorouracil and its 2, 3, 4, 5 -tetra-acetate/ 4,5,6-tri-0-benzoyl-2,3-di S-ethyl-... 

Alditols, Cyclitols and Derivatives Thereof. - 2,5 3,4-Dianhydro-D-altritol, 2,5-aohydro-3,4-0-(l,2-ethanediyl)-D mannitol, pentaerythritol tetraacetate, ribitol tetraacetate, xylitol tetraacetate, D-arabinitol tetraacetate, D, L-arabinitol tetraacetate, 2,4 3,5-di-0-isopropylidene-D-mannitol, 2 hexa-O-acetyl-D-mannitol, allitol hexaacetate, D-mannitol hexaacetate, D, L-mannitol hexaacetate, D-iditol hexaacetate, D, L-iditol hexaacetate, D, L-glucitol hexaacetate, D, L-altritol hexaacetate, L-galacto-D-galacto-decitol (which is C2-symmetric), 5 6-0-benzyl-2,3-0-[(S)-caniphanylidene]-l,4,5-tris-0-pivaloyl-D-myo-inositol, 6D-3,6-di-0-benzyl-l-0-[(S)-camphanyl]-2-deoxy-2,2-difluoro-4,5-0-isopropylidene- y< -inositol, cyclopentane 28. ... 

Alditols. Cvclitols and Derivatives Thereof.- D-Arabinitol, D-altritol, Ti-gtycero-H-mcmno-and D-g/ycero-D- /Mco-heptitols, D-g/yc ro-L-ga/acro-hcptitol, racemic perseitol (D-g/yccro-D- fl/octo-heptitol and its enantiomer), 4-0-P-D-galactopyranosyl-D-glucitol dihydrate (lactitol), hexa-O-acetyl-D-glucitol," " penta-0-acetyl-xylitol," and methyl 1,5-di-O-acetyl-3,4-bis-0-(bicyclophosphoranylato)quinate. ... 

Acyclic Alditols.- A new approach to the synthesis of optically pure polyhydroxylated compounds by i) the stereospecific reduction of chiral -ketosulphoxides and ii) the stereospecific liydroxylation of chiral allylic /9-hydroxysulphoxides has been described. Thus the unsaturated ester (1) gave the chiral sulphoxide (2), which was sequentially reduced, hydtoxylated, and further reduced as outlined in Scheme 1 to give the L-arabinitol derivative (3) and hence penta-0-acetyl-L-arabinitol in high yield enantiomers are available by appropriate choice of the sulphoxide reagent. ... 

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