Carbohydrates anomeric carbon

The two stereoisomeric furanose forms of d erythrose are named a d erythro furanose and p d erythrofuranose The prefixes a and p describe fhe relative configu ration of fhe anomeric carbon The configurafion of fhe anomeric carbon is compared wifh fhaf of fhe highesf numbered chiralify cenfer m fhe molecule—fhe one fhaf defer mines whefher fhe carbohydrafe is d or l Chemisfs use a simplified informal version of fhe lUPAC rules for assigning a and p fhaf holds for carbohydrates up fo and mclud mg hexoses... 

Orienf fhe Haworth formula of the carbohydrate with the ring oxygen at the back and the anomeric carbon at the right... 

For carbohydrates of the d series the configuration of the anomeric carbon is a if Its hydroxyl group is down p if the hydroxyl group at the anomeric carbon IS up... 

Glycosides are a large and very important class of carbohydrate derivatives character ized by the replacement of the anomeric hydroxyl group by some other substituent Gly cosides are termed O glycosides N glycosides S glycosides and so on according to the atom attached to the anomeric carbon... 

Disacchandes are carbohydrates that yield two monosaccharide molecules on hydroly SIS Structurally disaccharides are glycosides m which the alkoxy group attached to the anomeric carbon is derived from a second sugar molecule... 

The most important derivatives of pyrimidines and purines are nucleosides Nucleosides are N glycosides m which a pyrimidine or purine nitrogen is bonded to the anomeric carbon of a carbohydrate The nucleosides listed m Table 28 2 are the mam building blocks of nucleic acids In RNA the carbohydrate component is d ribofuranose m DNA It IS 2 deoxy d ribofuranose... 

Anomeric effect (Section 25 8) The preference for an elec tronegative substituent especially a hydroxyl group to oc cupy an axial orientation when bonded to the anomeric carbon m the pyranose form of a carbohydrate Anti (Section 3 1) Term describing relative position of two substituents on adjacent atoms when the angle between their bonds is on the order of 180° Atoms X and Y m the structure shown are anti to each other... 

The most familiar of all the carbohydrates is sucrose—common table sugar. Sucrose is a disacchar ide in which D-glucose and D-fructose are joined at then anomeric carbons by a glycosidic bond (Figure 25.7). Its chemical composition is the same ine-spective of its source sucrose from cane and sucrose from sugar beets are chemically identical. Because sucrose does not have a free anomeric hydroxyl group, it does not undergo mutarotation. 

Anomeric effect (Section 25.8) The preference for an electronegative substituent, especially a hydroxyl group, to occupy an axial orientation when bonded to the anomeric carbon in the pyranose form of a carbohydrate. 

The anomeric-carbon region shows six peaks, numbered in Fig. 4. Peak 1 (at 103.6 p.p.m.), which arises from 25 5 carbon atoms, can be assigned to the anomeric-carbon atoms of a-D-mannopyranosyl units, having free hydroxyl groups at C-2, that are involved in glycosidic linkages to 0-2 or 0-3 of other a-D-mannopyranosyl residues.15 Peak 2 (at 102.5 p.p.m.) probably arises from 2-O-substituted a-D-mannopyrano-syl units involved in linkages to 0-2 or 0-3 of other a-D-mannopyranosyl units (internal carbohydrates)15 and also to the anomeric carbon atom of the a-D-mannopyranosyl residue linked to L-threonine.19 Peak 3 (101.8 p.p.m.) arises from the a-D-mannopyranosyl unit linked to L-ser-ine.19... 

Table XVIII contains the 13C-n.m.r.-spectral data for the model compounds a,/ -Araf — Hyp and a,/ -Ara/— Hyp. The assignments of Qfi and Cs of Hyp were readily obtained19 by comparison with 13C data for L-Hyp in the free amino acid form and for L-Hyp residues of peptides.109 The chemical shift of C 5 was, as expected, 7-8 p.p.m. downfield from the values reported for nonglycosylated L-Hyp. The chemical shifts of C and Cy appeared in the same region as carbohydrate resonances and were therefore identified through their chemical shift-pH dependence.19 The chemical shift of the / -anomeric carbon atom in compound 60 is rather up-field, in agreement with a syn orientation for the C-1 - O-1 and...

We report here some literature examples 13, 55 of A-vinylsulfonylation and reduction to A-vinyl derivatives. Reactions were applied to different types-fused, anchored, spiro-OZTs on carbohydrate scaffolds and the examples shown indicate that the location of the OZT moiety with respect to the anomeric carbon can sometimes influence the results obtained. 

Roberts and co-workers have employed a number of chiral carbohydrate-derived thiols as polarity reversal catalysts in the radical hydrosilylation of electron-rich prochiral alkenes [68-70]. In these thiols, the SH group is attached to the anomeric carbon atom. Scheme 21 demonstrates the non-catalyzed reaction and in step b, the hydrogen atom transfer from the silane... 

A glyeosidic bond is formed by a condensation reaction between an alcohol and the nydroxyl group of the anomeric carbon of a carbohydrate. 

Fig. 1 also may be used to note some general characteristics of C spectra of carbohydrate polymers ( -11) Chemical shifts of anomeric carbons (C-l), in the region of 100-110 p.p.m., are typically well separated from other signals. As compared with C-l of the related monosaccharides (12-15)j the anomeric carbon is strongly deshielded (commonly by 7-10 p.p.m.) through glycoside formation (9)> i.e., by the change from 0-H to an 0-C bond. 

---