5- Deoxy-D-arabinitol

Enders and Jegelka [88] have used l,3-dioxan-5-one 122, a protected dihydroxyacetone derivative, to construct enantiomerically pure C5- to C9-deoxycarbohydrates. For example, reaction of 122 with SAMP gives the hydrazone 123, which is deprotonated and alkylated with methyl iodide to yield 124. The monoalkylated hydrazone is then alkylated in the same manner with chloromethyl benzyl ether to form 125. Cleavage of the hydrazone with ozone furnishes the protected ulose 126 (>98% de, >98% ee), which is deprotected to (—)-5-deoxy-L-r/ir o-3-pentulose 127. Reduction of 126 with L-Selectride, followed by deprotection, provides 5-deoxy-D-arabinitol 128 (>95% de, >95% ee) (Scheme 13.46). 

L-Selectride LiB[CH(CH3)C2H5]3H SCHEME 13.46 Enders synthesis of 5-deoxy-D-arabinitol. 

Constit. of the fruit of Glehnia littoralis. Syrup, [a] -23 (c, 1.1 in MeOH). This is 5-deoxy-D-arabinitol or 1-deoxy-D-lyxitol. The former takes preference acc. to the lUPAC special nomenclature rules for carbohydrates. 

Tetra-Ac 1,2,3,4-Tetra-0-acetyl-5-deoxy-D-arabinitol. 2,3,4,5-Tetra-O-acetyl-l -deoxy-D-lyxitol [90129-06-9]... 

Dtbenzylidene l,2 3,4-Di-0-benzylidem-5-deoxy-D-arabinitol C19H20O4 312.365 Needles (EtOH). Mp 143-146°. 

Di-O-benzyI-L-ri7 0 -hexos-5-ulose, H-KG 2,3 4,5-Di-0-benzylidene-D-alIitol, A-75 2,3 4,5-Di-0-benzylidene-D-arabinitol, A-792 2,3 4,5-Di-0-benzylidene-D-arabinose diethyl dithioacetal, A-852 2,4 3.5-Di-0-benzylidene-D-arabinose diethyl dithioacetal, A-852 1,2 3,4-Di-0 -benzylidene-5-deoxy-D-arabinitol, D-40 2,3 4,5-Di-0 -benzylidene-1 -deoxy-o-xylitol, D-385 2,3 4,5-Di-0-benzylidene-l-deoxy-DL-xylitol, D-385 3,5 4,6-Di-D-benzylidene-I,2-dideoxy-L-xyfo-hex-l-enitoI, D-579 l,3 4,6-Di-0-benzylidene-2,5-di-0-mesyl-i>mannitoI, M-25... 

Dianhydro-l-deoxy-4-0-mesyl-D-glucitol, D-492 2,5 3,6-Dianhydro-l-deoxy-4-0-tosyl-D-glucitol, D-492 1,2 3,4-Di-0 -benzylidene-5-deoxy-D-arabinitol, D-40 l,2-Dideoxy-am6mo-hexitol Y>-form, D-595 i>-erythro iorm, T-176 moM K) 2-Heptulose D-form 1-Deoxy, H-62 Methyl l-deoxy-D-r/6o-2-hexulopyranoside, D-222... 

Di-0 -benzylidene-5-deoxy-D-arabinitol, D-40 2,3 4,5-Di-0-benzylidene-l-deoxy-D-xylitol, D-385 2,3 4,5-Di-O-benzylidene-l-deoxy-DL-xylitol, D-385 2,3 4,5-Di-O -benzylideneribitol, R-94... 

Di-anhydro-pentitols (14) and (15) have been prepared from 1,4-anhydro-5-chloro-5-deoxy-D-arabinitol and -D-xylitol respectively, and another paper has described a similar synthesis of the L-enant-iomer of (15) together v ith oxetans of 2,5-anhydro-hexitols and the dioxetans (16) and (17), ... 

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. 

If the nitrile 66 is treated with 5.5% methanolic ammonia, 1,1-bis-(benzamido)-l-deoxy-D-arabinitol (68) is obtained, whereas the same concentration of ammonia in isopropyl alcohol gives60 compound 67. When this reaction was conducted (employing 5.5-8% of ammonia in methanol or isopropyl alcohol) with perbenzoylated D-galactono-nitrile, and with the perbenzoates of D-glucopyranose, D-galacto-... 

Acetamido-5-deoxy-D-threo-pentulose and 5-acetamido-5-deoxy-L-erythro-pentulose (204) are obtainable by the bacterial oxidation of 1-acetamido-l-deoxy-D-arabinitol and 1-acetamido-l-deoxy-D-ribitol, respectively. Both ketoses are crystalline, and show a strong carbonyl vibration in their infrared spectra. Accordingly, they exist in the acyclic form. Their isopropylidene acetals are likewise acyclic. Furthermore, 5-acetamido-5,6-dideoxy-L-xylo-hexulose (205), obtainable by bacterial oxidation, shows a great tendency to assume the acyclic structure. 5-Acetamido-5-deoxy-L-xi/io-hexulose (206) may be obtained by the bacterial oxidation of 2-acetamido-2-deoxy-D-glucitol it assumes, exclusively, the sterically more-favored pyranose form. ... 

Reductive amination of 5-azido-2,3-di-0-benzyl-5-deoxy-D-arabinofuranose afforded 2,3-di-0-benzyl-l,5-dideoxy-l,5-imino-D-arabinitol from which the hydroxymethyl derivative 37 has been prepared (via hydroboration of the 4-C-methylene analogue) together with its C-4 epimer as a minor constituent. The hydroxymethyl group in 37 was further oxidized to a carboxylic acid function and the resulting product was found to be a good inhibitor of P-glucosidase. ... 

O-BenzyIideneribitol, R-94 Clusianose, C-142 1-DeoxyarabinitoI D-form, D-39 1-DeoxyarabinitoI D-form, D-39 5-DeoxyarabinitoI D-form, D-40 5-Deoxyarabinitol DL-form, D-40 3-Deoxy-D-arabinitol, P-27... 

Tetra-0-acetyl-5-deoxy-DL-arabinitol, D-40 Tetra-O-acetyl-l-deoxy-D-ribitol, D-356... 

Tetra- O -benzoyl-5-deoxy-DL-arabinitol, D-40 Tetrahydro-3-hydroxy-5-hydroxymethyl-3-furancarboxylic acid, T-26... 

R = H 3.5-Q-benzylidene-l-deoxy-2-C-phenyl-D-arabinitol yield 77% d.r. (39/40) 100 0 40 R = TBDMS 3,5-0-benzylidene-4-0-tert-butyldimethylsilvl-t-deoxy-2-C-phenyl-D-ribitol yield 89% d.r. (39/40) 0 100... 

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