Monosaccharides branched-chain

Branchand and coworkers have used cobriloximes as alkyl rathcM precursors for the cross-conphng reacdon v/ith rutronates." This method Is very useful for producing branched-chain monosaccharides, as shovm in Eq. 5.39." ... 

This is a modified form of the 1980 recommendations [4]. Priority is now given to naming cyclic forms, since in most cases branched-chain monosaccharides will form cyclic hemiacetals or hemiketals. 

A branched-chain monosaccharide is named as a substituted parent unbranched monosaccharide, as outlined in 2-Carb-16.1 to 2-Carb-16.4. 

Chart V. Choice of parent in branched-chain monosaccharides. In the first names given for examples 1,3 and 4, side-chain configuration is specified by use of R and S. This approach is generally preferred in all but the simplest cases, as less open to misinterpretation. 

IUPAC-IUB Joint Commission on Biochemical Nomenclature (JCBN), Nomenclature of branched-chain monosaccharides (Recommendations 1980), Eur. J. Biochem., 119, 5-8... 

This group includes a set of anionic polysaccharides secreted by unrelated bacteria. The common theme, however, is that their main chains have the same tetrasaccharide repeat. Although (high acyl) native gellan (42) and (deacylated) gellan (40,41) are linear polymers, welan (43) is a branched polymer in which a monosaccharide side chain is regularly attached to each repeat. Other members of this family, such as S-657 and rhamsan, are also branched, like welan."0... 

A further complication that may be encountered in the nomenclature of branched-chain monosaccharides is in the numbering of the carbon atoms of the molecule. There is some precedent for numbering the carbon atoms of the branched moiety continuously with the carbon atoms of the main chain. However, this can result in confusion and ambiguity, especially when there are further substituents on the branched carbon atoms. In this connection, the Geneva system of nomenclature11 provides a reasonable solution, which is illustrated in the naming of compounds XII10 and XIII. 

Dondoni pioneered the use of 2-(trimethylsilyl)thiazole (71) as a formyl anion equivalent for the homologation of aldehydes. Extension of this reaction to ketones would be very useful, but has thus far been restricted to tritluoromethyl cases. However, it has now been widened to include several a, a -alkoxy ketones, as demonstrated in a new route to branched-chain monosaccharides. Aldehydes catalyse the reaction, although the scope is still limited electrophilic aldehydes, such as 2-fluorobenzaldehyde, promote the addition of (71) to electrophilic ketones. 

Polysaccharides that are formed from only one type of monosaccharide are called homo-glycans, while those formed from different sugar constituents are called heteroglycans. Both forms can exist as either linear or branched chains. 

Eur. J. Biochem. (1980) 111, 295-298 Nomenclature of unsaturated monosaccharides Eur. J. Biochem. (1981) 119, 1-3 Nomenclature of branched-chain monosaccharides Eur. J. Biochem. (1981) 119, 5-8 Abbreviated terminology of oligosaccharide chains /. Biol Chem. (1982) 257, 3347-3351 Polysaccharide nomenclature /. Biol Chem. (1982) 257, 3352-3354 Symbols for specifying the conformation of polysaccharide chains... 

A novel synthesis of branched-chain monosaccharides was based on the finding that 3-furoic acid readily undergoes Birch reduction, affording 2,3-dihydro-3-furoic acid. Treatment of its methyl ester 398 with methanol and acid gave,264 in quantitative yield, methyl tetrahy-dro-5-methoxy-3-furoate 399 as a mixture of the isomers. Compounds... 

FIGURE 7-13 Homo- and heteropolysaccharides. Polysaccharides may be composed of one, two, or several different monosaccharides, in straight or branched chains of varying length. 

Branched-chain monosaccharides have now been detected as components of bacterial polysaccharides. The known examples include yersiniose [3,6-dideoxy-4-C-(hydroxyethyl)-D-xy/o-hexose228] from Y. pseudotuberculosis, a 3-C-(hydroxymethyl)pentofuranose from Coxiella bumetti,229 and 6-deoxy-3-C-methylhexoses from the same organism and from Nitrobacter hamburgiensis.229 Several branched-chain monosaccharides were identified as components of antibiotics, and the pathways of their biosynthesis in bacteria were studied. These investigations were discussed in detail by Grisebach in this Series.230 The usual precursors for the formation of the monosaccharides of this group are the nucleoside 6-deoxyhexosyl-4-ulose diphosphates 7a and 7b. 

Monomers and polymers of carbohydrates, (a) The most common carbohydrates are the simple six-carbon (hexose) and five-carbon (pentose) sugars. In aqueous solution, these sugar monomers form ring structures, (b) Polysaccharides are usually composed of hexose monosaccharides covalently linked together by glycosidic bonds to form long straight-chain or branched-chain structures. 

Naturally occurring polysaccharides can occur either as individual carbohydrate molecules or in combination with other naturally occurring substances, such as proteins (glycoproteins) and lipids (glycolipids). In all cases the polysaccharide section may have linear or branched chain structures, which often contain the derivatives of both monosaccharides and aminosugars (Figure 1.20). 

Synthesis of Branched-Chain Monosaccharides from Cs-Aldoses... 

Most of the methods presented for the de novo synthesis of linear monosaccharides can be used to prepare branched-chain sugars and analogs and some examples are given above and below. The branched-chain aminolactone 222 was prepared by two-carbon chain elongation via addition of 221 to 2,3-0-isopropylidene-L-glyceraldehyde (Scheme 13.69) [126]. 

SCHEME 13.71 Syntheses of branched-chain monosaccharides starting from (5 )-2-benzyloxypropanal. 

Hemicelluloses are a family of four basic types of polysaccharides, composed of two or more monosaccharide residues. All have structural features similar to cellulose in that they have their main chains that are -(1 4) linked, with the exception of the arabinoglactans that are /3-(l—>3) linked. The main chains are homopolysaccharides composed of a single monosaccharide residue, but they are highly branched by one or two different kinds of monosaccharides that are linked for the most part to give single monosaccharide branches. 

In O Scheme 1, O Scheme 2 and O Scheme 3, some of the important representatives of natural monosaccharides are presented and compiled by the three different classes deoxy-sugars, amino-sugars, and branched-chain sugars. O Table 1 lists their names and natural sources of occurrence. 

---