Mannitol, 1-Deoxy

Support for this result was obtained from the taste of 1,5-anhydrohexitols, which, only for purposes of comparison, can be regarded as 1-deoxyal-dopyranoses. 1,5-Anhydro-D-glucitol (that is, the incorrectly named 1-deoxy-D-glucopyranose ) (14), 1,5-anhydro-D-mannitol ( 1-deoxy-D-mannopyranose or 2-deoxy-D-fructopyranose ) (15), and 1,5-anhydro-D-galactitol ( l-deoxy-o-galactopyranose ) (16) are all purely sweet, without any trace of bitterness. Furthermore, the complete absence of bitterness of 1,5-anhydromannitol (16) clearly indicates that the anomeric... 

Methyl mannoside Mannosaminitol JV-Acetylmannosamine -Acetylmannosaminitol Anhydro Mannitol Deoxy... 

Aliphatic fluorodenitration has also been applied to mononitro compounds, specifically to an a-nitroepoxide Thus, l,2-anhydro-3 4 5,6-di-O isopropyli dene-1-C-nitro D mannitol and labeled potassium bifluonde give 2-deoxy-2-fluo-ro-3,4 5,6-di-O-isopropylidene aldehydo D glucose [J03, 104] (equation 30)... 

L-Rhamnitol (L-Rha-ol) or 1-deoxy-L-mannitol 2-Carb-19.2. meso Forms... 

Amino-1,5-anhydro-1 -deoxy-D-mannitol or 1,5-dideoxy-1,5-imino-D-mannitol trivial name deoxymannojirimycin... 

Deoxy-4-fluoro-D-fructose (552) was prepared (59%) by fermentation of 3-deoxy-3-fluoro-D-mannitol with Gluconobacter oxydans. The structure of 552 (fi-T) form) was confirmed by the n.m.r. spectrum, which resembles that of 4-deoxy-4-fluoro-Q -D-sorbopyranose (553) 552 was identical with one of the products obtained from the oxirane-ring opening of 3,4-anhy-dro-l,2-0-isopropylidene- -D-tagatopyranose with KHFj. 

When Shallenberger and coworkers attempted to explain the sweetness of /8-D-fructopyranose, they intuitively assigned the anomeric 2-hydroxyl group as AH and the oxygen atom of the 2-(hydroxymethyl) substituent as B. This assignment has since been supported by Lindley and Birch. It was shown that 1,5-anhydro-D-mannitol (15, 2-deoxy-D-fructopyranose ) and jS-D-arabinopyranose (22) (in both of which, one of the AH or B units... 

Fom- title compounds, 5-deoxy KDG Me estw, 5-epi KDG Me ester, 4-0-Me KDG Me ester and 4-deoxy KDG Me ester were prepared either from D-glucono-l,5-lactone or from 1,2 5,6 di-O-isopropylidene-D-mannitol. Biological tests perfcHined rat these molecules have shown that the compounds modified on the C-5 position (5-deoxy KDG Me ester and 5-epi KDG Me ester) are gratuitous inducers of the e>q>ression of pectinase genes in the phytopathogenic bacteria Erwinia Chrysanthemi when the C-4 modified molecules (4-0-Me KDG Me ester and 4-deoxy KDG Me ester) are not inducers. 

Ana,6s (2 AM6S (where I = a-L-iduronic acid, ANA6S = 2-acetamido-2-deoxy-a-D-glucopyranose 6-sulfate, G = / -D-glucuronic acid, and AMes = 2,5-anhydro-D-mannitol 6-sulfate, the last arising from 2-deoxy-... 

The alcoholysis of the cyclic phosphate of catechol by alditols can lead, after acid hydrolysis of intermediate, cyclic phosphates, to the selective formation of phosphoric esters of the primary hydroxyl groups in the alditols. Thus, erythritol and D-mannitol afford, after chromatographic purification of the reaction products, their 1-phosphates in yields of 31 and 38%, respectively.217 The method was used to convert riboflavine into riboflavine 5 -phosphate.218 1-Deoxy-1-fluoro-L-glycerol has been converted into the 3-(dibenzyl phosphate) in 54% yield by selective reaction with dibenzyl phosphorochloridate. 219... 

Intramolecular displacement of primary sulfonyloxy or halide groups in derivatives of D-mannitol can also be brought about under basic conditions, albeit in low yield. Treatment of l,6-di-0-(methyl-sulfonyl)-D-mannitol (78), or the corresponding dichloride derivative, with sodium methoxide gave 2,5 3,6-dianhydro-D-glucitol74 (79). Treatment of the latter with hydrochloric acid at 100° in a sealed tube gave the 6-chloro-6-deoxy derivative (80), which was converted into the known 2,5-anhydro-l,6-di-0-benzoyl-D-glucitol45 47 (32). The sequence 78-80 is of interest in the context of C-/3-D-nucleoside precursors, but it suffers from the fact that yields are low. 

Examples of other fluorinated inhibitors, mainly of D-glucosidases, are the 2-deoxy-2-fluoro derivative 106 (Scheme 27) of miglitol (A-hydroxyethy I -1 -deoxynoj i i i my-cin, 107),229 4-deoxy-4,4-difluoroisofagomine (108),230 3-deoxy-3-fluoro-calystegin B2 (109),231 the 1-deoxyfluoro derivative (110) of 2,5-dideoxy-2,5-imino-D-mann-itol,232 as well as the 3-deoxyfluoro analogue (111) of nonnatural l-DMDP (2,5-dideoxy-2,5-imino-L-mannitol)233 and the 3-deoxy-3,3-difluoro derivative (112) of 2,5-dideoxy-2,5-imino-D-glucitol (113).234 All of these are weaker inhibitors than the parent compounds. l,4,6-Trideoxy-6-fluoro-l,4-imino-D-mannitol (114) was prepared by Winchester and coworkers.210... 

G. Legler and E. Jiilich, Synthesis of 5-amino-5-deoxy-D-mannopyranose and l,5-dideoxy-l,5-imino-D-mannitol, and inhibition of a- and P-D-mannosidases, Carbohydr. Res., 128 (1984) 61-72. 

Dideoxy-2,5-imino-D-mannitol (26), a nattural product found in Derris elip-tica as well as Lonchocarpus sp. [126], was obtained from L-sorbose via 5-azido-5-deoxy-D-ffuctopyranose (82) by Card and Hitz [127] and characterized as a very potent inhibitor of /3-D-fructofuranosidase (invertase). 

If an appropriately situated, unsubstituted hydroxyl group is available, anhydro-ring formation usually takes precedence over substitution or elimination. Thus, with alkali, the bromo-, chloro-, and iodo-deoxy sugars react analogously to sulfonic ester derivatives148 to afford epoxides in good yield.22,169 It has been established170 that l,2 5,6-dianhydro-D-mannitol is formed in aqueous solutions of... 

In a different synthesis of 1,5-anhydrohexitols from a compound having a pyranoid ring, Lehmann and Friebolin31 treated 1,5-anhydro-2-deoxy-D-arafemo-hex-l-enitol (D-glucal) (20) with a-toluenethiol in the presence of light, and obtained l,5-anhydro-2-S-benzyl-2-thio-D-mannitol (21) and the epimeric anhydro-D-glucitol in equal amounts. 

Tri-0-acetyl-l,5-anhydro-2-deoxy-D-arabino-hex-l-enitol (tri-O-acetyl-D-glucal) was the starting point for the synthesis of 1,5-anhy-dro-2-chloro-2-deoxy-D-glucitol or -D-mannitol by way of the 1,2-dichloride (22), which was reduced32 by means of lithium aluminum hydride to the 2-chloro-2-deoxy derivative (23). That the chlorine... 

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