Acids Derived from Sugars

Through oxidation of the terminal aldehyde and alcohol functions of monosaccharides four different types of polyhydroxycarboxylic acids can be generated for which numerous traditional names are in use (see Table 17). Systematic names for these compounds, though, can very simply be formed by appropriate transformations or replacements of the. ..ose and. .. ulose endings as shown below  

Derivatives of these acids are named in accordance with the general rules of substitutive nomenclature. 

O-Alkyl and 0-acyl derivatives of saccharides can most easily be named as such even though traditional ester names are still widely used for the latter. 

6-Di-O-phosphonato-a-D-fructofuranose or 1,6-Bisphospho-a-D-fructofuranose or a-D-Fructofu-ranose 1,6-bisphosphate 

The inevitable acronym ADP too comes from the ester name adenosine-5 -diphosphate customarily preferred to the systematic denominations 5 -0-(diphosphonato)adenosine or 5 -(diphospho)adenosine. 

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Constitutional Studies in the Monocarboxylic Acids Derived from Sugars. Part III. The Isomeric Tetramethyl Galactonolactones and Trimethyl Arabonolactones, J. Pryde, E. L. Hirst, and R. W. Humphreys, J. Chem. Soc., 127, 348 (1925). 

Citric acid derived from sugars by fermentation can be converted to methacrylic acid with hot water (as mentioned in Chap. 8). Acrylonitrile (a carcinogenic monomer) is made by the oxidation of propylene with a mixture of ammonia and oxygen.21... 

Similar polyacetal structures were prepared by BASF scientists from general dialdehydes and aliphatic hydroxycarboxylic acids derived from sugars [156, 157], shown in Scheme 15. Alternatively, carboxypolyacetals are available by the addition of polyhydroxy carboxylic acids, tartaric acid, for example, to divinyl ethers [158]. 

Fig. 15.5. Carboxylic acids derived from sugars (in part modified from Goodwin and Mercer, 1983 used with permission of the copyright owner, Pergamon Press, Oxford).

Alpha-hydroxy acids or fruit acids are glycolic acid derived from sugar cane, lactic acid from sour mUk, citric acid from citrus fruits, malic acid from apples, and tartaric acid from grapes. 

An unusual citric acid derivative is toxic agaricinic (agaric) acid, which occurs in some fungi (see 10-241). Foods also contain numerous hydroxy acids derived from sugars. 

There is continued interest in chiral syntheses of pyrrolidines, piperidines, and related bicyclic systems. A review has appeared, in Russian, on the stereoselective synthesis of proline and pipecolic acid derivatives from sugars. The antifungal pyrrolidine (+)-preussin (74) has been made from the glucose-derived epoxide (73) as indicated in Scheme 16,58 whilst... 

Conversion to carbamates. Cyclic carbamates derived from sugars and related compounds have repeatedly been encountered, the first being an inosamine derivative, obtained by Curtius degradation of dihydroshikimic acid.82,83... 

As early as 1917, it was known that C2 and C3 in this trimethyl sugar each carried a methoxyl group, since (a) it failed to yield an osazone, and (b) the trimethyl-D-glucoheptonic acid derived from it by a cyanohydrin synthesis gave a lactone only with the concomitant loss of one of the methyl radicals.135 The production of a dimethyl- and not a trimethyl-... 

Fluoroalkyl Glycosides (RFn-(CH2)2-n-0-sugar) and Perfluor-oalkylidene Acetals Derived from Sugars The very low nucleophilicity of fluoroalcohols makes it difficult to substitute of a hydroxyl (anomeric or not). ° This is the reason why this type of ether is not very common. Such ethers have only been isolated in very small quantities in solvolysis reactions, or in carben insertions, performed in fluorous alcohols.Preparation of these ethers has been solved by means of the Mitsunobu reaction. This reaction is known to be dependent on the pA a of the acceptor of the glycosyl the acidity of fluorous alcohols allows a much easier deprotonation than with non fluorinated alcohols." ... 

Section V contains specific examples of procedures for Inflate synthesis some general comment about these procedures is worthwhile. Triflic anhydride is the reagent of choice for preparing triflates derived from sugars, whereas triflyl chloride is used more often when uucleosides are involved. Triflate formation with triflic anhydride requires addition of a base (usually pyridine) to the reaction mixture to neutralize the triflic acid produced [Eq. (4) 7]. Some triflates are reactive enough that pyridine can function as a nucleophile in the substitution process. In these instances, replacement of pyridine with a non-nucleophilic base, such as 2,6-di-r-butyl-4-methylpyridine, avoids this undesired reaction (Scheme 1) [7]. 

Alkylation of the salicylamide 168 with 2-bromoacetophenone 169, followed by the acid-mediated (/>-toluenesulfonic acid, PTSA) cyclocondensation of intermediate 170 under Dean-Stark reflux conditions, gave 55-90% of the oxazepinones 171 (Scheme 27) <2002BML2367>. A related example leading to benzoxazepin-5-ones has been reported <1995T13301>. Tetracyclic benzoxapinones derived from sugars were prepared by intramolecular nucleophilic substitution of fluorine <20010L1089>. 

A nice extension of this protocol is the use of <5, -unsaturated aldehydes derived from sugars such as D-glucose and D-ribose to yield polyhydroxylated condensed dihydropyrans [18]. Good results were obtained using N,N-dimethylbarbituric acid... 

Fischer applied the Kiliani procedure (Scheme 1.1) to arabinose 5, an aldopentose obtained from sugar beet, and this produced the enantiomer 6 of the hexonic acid derivable from natural glucose (Figure 1.4). This observation led to the conclusion that the D-enantiomers of arabinose, glucose, mannose, and fructose all share the same configurations at their three highest numbered chiral centers. Moreover, the arabinose obtained from beet was the L-isomer. 

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