Alditols derivatives

Reddy, G. P. and Bush, C. A., High-performance anion exchange chromatography of neutral milk oligosaccharides and oligosaccharide alditols derived from mucin glycoprotein, Anal. Biochem., 198, 278, 1991. 

In the course of their studies of pseudouridine,164 Asbun and S. B. Binkley183 reported the synthesis of 5-/3-D-arabinofuranosyl- and 5-/3-D-xylofuranosyl-uracil (258 and 259) by the acid-catalyzed ring-closure of the corresponding alditol derivatives. The configuration at the anomeric carbon atom was determined on the basis of optical rotatory dispersion studies. 

In addition to these physical studies at the Bureau, Tipson was able to return to his synthetic interests, both alone and in collaboration with other staff members. He was especially pleased to prepare D-talose in crystalline form, an accomplishment that had eluded Emil Fischer. Pursuing his longstanding interest in the reaction of sulfonic esters with iodide and following an earlier observation that the tetratosyl ester of erythritol is converted into butadiene by the action of sodium iodide and zinc, he demonstrated (with A. Cohen) that nonterminal unsaturation may be conveniently introduced into alditol derivatives by reaction of contiguous secondary sulfonates with sodium iodide and zinc dust in boiling A.A-dimethylformamide. This Tipson-Cohen reaction subsequently proved of great utility in other hands for the conversion of more complex carbohydrate structures into vicinal dideoxy derivatives. 

Among them are found the naturally occurring 1-deoxynojirimycin (DNJ) and 1-deoxymannojirimycin (DMJ) [96]. Practical syntheses of DNJ and DMJ start from L-gulono-1,4-lactone (20b) and o-mannono-1,4-lactone (74), respectively [97]. Key intermediates are 2,6-dibromo-2,6-dideoxy-D-alditol derivatives 75a and 75b obtained by 2,6-dibromination of the starting lactones, followed by reduction with NaBH4 [98, 99]. Then a five-step sequence involving selective partial protection, introduction of an amine functionality, and intramolecular N-alkylation, lead to DNJ and DMJ, respectively (Scheme 22). 

The class includes alditol derivatives (such as acetates and methyl (38) O. S. Chizhov, L. S. Golovkina, and N. S. Wulfson, unpublished data. 

Unless otherwise noted, acetone was the solvent. 6 Yield of monodeoxy-monoiodo-alditol derivative. Yield of dideoxy-diiodo-alditol derivative. d Yield of sodium sulfonate. Free iodine liberated. i Acetonylacetone. Plus sodium bicarbonate to prevent cleavage of the benzylidene group. Acetic anhydride. 

Action° of Sodium Iodide on Alditol Derivatives Having a Secondary Sulfonyloxy Group Contiguous to a Primary Sulfonyloxy Group... 

Oldham and Rutherford s Rule does not apply to, nor was it propounded for, non-cyclic alditol derivatives. Neither does it apply to that part (if any) of a cyclic-sugar molecule which is actually an appended, non-cyclic alditol chain. Thus, it does not apply to carbon atoms 5 and 6 of an aldohexofuranose nor, presumably, to carbon atoms 6 and 7 of an aldoheptopyranose or carbon atoms 5, 6, and 7 of an aldoheptofuranose. 

FIGURE 5.2 The alditols derived from the C4, C5, and C6 monosaccharides in the D-series. Degenerate symmetry means that there are only three pentitols and six hexitols. 

SCHEME 13.21 Desymmetrization of meso-diacetate by lipase-catalyzed hydrolysis synthesis of C3-alditol derivatives. 

In the alditol derivative 3-0-benzyl-l,2 5,6-di-0-isopropylidene-4-0-(methylsulfonyl)-n-mannitol (40), both Foster and coworkers and Baker and Haines observed intramolecular displacement by the benzoate group. Foster and coworkers employed sodium benzoate in moist, boiling N,N-dimethylformamide, whereas Baker and Haines used sodium acetate in moist iV,iV-dimethylformamide. An appreciable quantity of the Sk2 products, the 3,4-di-O-benzoyl-n-tabtol and the 4-0-acetyl-3-0-benzoyl-n-talitol derivatives, respectively, were noted in the resulting mixture. The monobenzoate fraction (42) results from attack by water on the... 

Alditol derivatives having terminal double bonds have frequently been prepared by treatment of vicinal, primary-secondary disul-... 

Further examples of l-phenylazo-l,2-unsaturated alditols derived by acetylation of aldose phenylhydrazones have been described,172 and a dimer, namely, l,2-bis(penta-0-acetyl-D-gluconoyl)ethylene (92), formed by way of a carbene intermediate, was reported to be... 

VIII. Unsatubated Acyclic Compounds 1. Alditol Derivatives... 

Alditol Derivatives Having Terminal Olefin Oroupings... 

Alditol derivatives containing non-terminal double bonds have also been reported. Treatment of 1,2 5,6-di-0-isopropylidene-3,4-di-O-p-tolylsul-fonyl-D-mannitol with sodium benzoate in iV,A -dimethylformamide afforded, in addition to saturated products of displacement, 3-deoxy-1,2 5,6-di-0-isopropylidene-4-0-p-tolylsulfonyl-D-(/ireo-hex-3-enitol and the corresponding tetrol formed by hydrolysis of the acetal rings. 1,2 5,6-Di-O-isopropylidene-D-mannitol and -D-altritol have been converted into the trans and cis isomers, respectively, of 1,2 5,6-di-O-isopropylidene-3,4-dideoxy-D-(/irco-hex-3-enitol by the thionocarbonate method. ... 

Among various strategies towards ulosonic acids various acylation reactions are often used. They involve alditol derivatives as convenient substrates, and diverse acyl anion equivalents. Here belongs the synthesis of KDO, developed by Shiba et al. [84], By reaction of the triflate 67 with the lithiated 68, eight carbon atoms compound 69 was obtained (Scheme 17). Removal of O-acetyl residue with subsequent NBS promoted oxidative hydrolysis of the dithioacetal moiety resulted in the formation of KDO derivative 70. 

I he formation of J i ion (shown in 3) is of particular significance in the mass spectra of oligosaccharide-alditol derivatives, and requires the pre.s-... 

The second major component obtained after HPLC (peak 5 of Fig. 2, O Neill and Selvendran, 1985b) on FAB-MS gave an ion at mIz 1200, corresponding to [M+1]" from a methylated alditol derivative containing two pentosyl, three hexosyl, and one hexitol residues. Using the principles outlined earlier, the sequence of the derivative was established... 

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