D-Glucitol derivatives

It is probable that the two 1,3-anhydro compounds just described are anhydrides of the same alditol. The compound of Ustyuzhanin and coworkers50 is unequivocally a 1,3-anhydro-D-glucitol derivative, because the hydroxyl groups at C-2, 4,5, and 6 were protected prior to the ring formation. Positive identity of the two would have been achieved by converting the monomethyl ether obtained by Haslam... 

These examples of radical-induced reduction of the isothiocyanato group indicate that the intermediate isocyanides 243a and 243b also undergo reduction, to 1,5-anhydro-D-glucitol derivatives 244a and 244b. 

At 1650, both tosyloxy groups in 108 were replaced with inversion, and the bis(dimethylamino)-D-glucitol derivative was obtained. On heating isosorbide (3) or its diacetate (111) in the presence of such dehydrating agents as aluminum oxide in a Pyrex-glass tube above 400°, the doubly unsaturated compound 112 is formed in —50% yield194 (see Scheme 23). 

On evaluating the behavior of 1,4 3,6-dianhydro-2,5-di-0-mesyl-D-mannitol (124) towards different nucleophiles, the doubly exchanged product 134 was mainly obtained,203 in addition to a small proportion of the D-glucitol derivative 135 (see Scheme 32). 

Alternatively, the synthesis of 5 has been effected from 2,3.4.6-tetra-O-benzyl-n-glucopyranose (59) (Schemes 9 and 10).61 Reduction of 59 afforded quantitatively the D-glucitol derivative 60.62 Swem oxidation of 60 gave 61, whose cyclization63... 

Both 2,5-anhydro-D-mannitol and 2,5-anhydro-D-glucitol contain the requisite 1,4-anhydro-D-arabinitol ring system.215-240 The D-mannitol derivative is about 3.5 times as potent an inhibitor as the D-glucitol derivative, perhaps by virtue of the fact that it may bind to con A either through the hydroxyl groups at C-l, C-3, and C-4, or C-3, C-4, and C-6 (compare Ref. 429). Finally, the important observation that methyl a-and /3-D-fructofuranoside are inhibitors (the (3 anomer being approximately three times as active as the a anomer) provides an explanation for the interaction of con A with plant and bacterial levans120-215-364 (see Section II,l,h). 

Rules (1) and (3) are extensions of the arguments used by Matheson and Angyal " to explain the behavior of the di-O-tosyl derivatives of the three dianhydrides toward sodium iodide. These authors found that, in the d-mannitol derivative, both tosyloxy groups are readily replaceable by iodine but in the D-glucitol derivative only one, and in the L-iditol derivative neither, tosyloxy group was replaceable. Wiggins and Wood had obtained a parallel series of results from reactions of the di-O-tosyl and di-O-mesyl... 

Roush s three-carbon chain-elongation method applied to 2,3-O-cyclohexylidene-D-glyceralde-hyde (R)-62 is an efficient approach to D-glucitol derivatives, which relies on the vyfx-selective epoxidation of homoallylic alcohol 170 (Scheme 13.59) [105,107]. 

SCHEME 13.59 Roush s conversion of D-glyceraldehyde into D-glucitol derivatives. 

Reduction of the 6-azido-6-deoxy-5-0-(4-tolysulfonyl)-D-glucitol derivative 32 gave the azirine acyclo C-nucleoside 33 (70MI10, 70MI11) (Scheme 3). 

Base-catalyzed intramolecular displacement of the 4-O-methylsulfony-loxy group in the D-glucitol derivative 1048 by the carbonyl of the 2-butyloxycarbonylamino group afforded the l,3-oxazin-6-yl C-nucleoside derivative 1050 (94T13299) (Scheme 303). 

Figure 8-4. Methylation analysis of in vitro P-D-glucans. (a) Gas chromatography of the permethyl-ated alditol acetate obtained from methylation analysis of the cellulose synthesized in vitro by the enzyme from blackberry. Peak 1, derivative characteristic of (1 4) linked glucosyl units. Peak 2, internal standard (mj o-inositol). The derivative characteristic of (1 3) linked glucosyl units usually elutes 1 min before the major derivative visible in the chromatogram (not shown see Bulone et al. 1995). (b) Structural characterization by electron impact mass spectrometry of the 1,4,5-tri-0-acetyl-2,3,6-tri-0-methyl-D-glucitol derivative corresponding to peak 1 in A and characteristic of (1 4) linked glucosyl units.

The di-aryl D-glucitol derivative (9) was one of the products isolated from reaction of D-glucose with phenol in acid solution (see also Chapter 3). 

Branched-chain di-C-methylpentltol derivatives (10) with the L-xylo-, L-rlbo, D-lyxo, and D-arabino-configuratlon, required for the synthesis of polyketlde-derlved natural products, have all been synthesized from the exo-methylene derivative (11). Photochemical addition of cyclohexene to aldehydo-D-glucose penta-acetate gave the 8-(pentltol-1-yl)-7-oxabicyclo[4.2.Oloctane derivative (12) in 65% yield.The 1,1-dl-C-substltuted-l-deoxy-D-glucitol derivative (13) was the major product from acid-catalysed... 

The l-amino-2-thio-D-glucitol derivatives (l8) have been... 

The 1-thio-D-glucitol derivative (9) has been obtained in three steps from 2,3,4,6-tetra-Q-benzyl-D-glucose by way of the tosylate (8). Mono- and di-sulphide bridged dimers (10) and (11)... 

D-Glucose has been converted to 1-thio-D-glucitol derivatives, including mono- and di-sulphide dimers.Stannic chloride reduction of the arabinoside benzyl ether (21) yielded the glyceryl-heterocycle (22)(Scheme 8) the paper discusses the mechanism of the reaction involved in detail.Nitroheptenitol derivatives undergo... 

During an attempt to a-metalate ( BuLi-TMEDA) at the carbon bearing the O-carbamate group in the l,4 3,6-dianhydro-D-glucitol derivative 18 in order to introduce bulky substituents with the purpose of obtaining improved chiral auxiliaries, an unexpected reaction took place leading to the formation of tihe 1,4-anhydro-D-xylb-enol carbamate derivative 19. It is likely that a-metalation occurred but was quickly followed by -elimination to form a stable alkoxide. ... 

The 1-amido-l-deoxy-D-glucitol derivative 23 has been prepared and shown to exhibit liquid crystal properties. ... 

A synthesis of 2,S-dideoxy-2,5-imino-D-glucitol (28) involves treatment of the D-glucitol derivative 29 first with acid resin in methanol (to remove the silyl and isopropylidene groups) then hydrogenolysis. Cyclization of the so-formed amino-mesylate to 28 surprisingly proceeds with retention of configuration and thus is likely to involve the 5,6-epoxide. ... 

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