Of aminodeoxy sugars

Ammonia, like carbon dioxide, is not over-common in periodate oxidation mixtures but it is quite important when it does appear, as in the oxidation of aminodeoxy sugars. The analysis for ammonia has been successfully performed using a Van Slyke-Neill apparatus,102 106 and by distillation and titration.78... 

Azidodeoxy sugars are useful intermediates in the synthesis of aminodeoxy sugars. Nucleophilic-displacement reactions of sulfonate and deoxyhalo derivatives of sucrose with sodium azide have been used for the preparation of sucrose azides. The reaction of... 

Prom the viewpoint of a synthesis chemist, carbohydrates would appear to be severely overfunctionalized. Thus, in a hexopyranose, one has to contend with five hydroxyl groups distributed over six carbon atoms. Furthermore, four of the hydroxyl groups are chiral. Obviously, to cany out synthetic manipulations on such molecules one has to learn to protect hydroxyl groups (or amino groups in the case of aminodeoxy sugars) to leave free only those destined for reactions. Therefore, a rich repertoire of protecting gronp manipulations for this purpose has evolved [1,2]. Table 1 shows some of the more common ones in current use. 

F. Pelyvds, C. Monneret, P. Herczegh, Synthetic Aspects of Aminodeoxy Sugars of Antibiotics, Springer-Veriag, Berlin, 1988. 

For the total synthesis of aminodeoxy sugars from nonsugar precursors, it is logical to turn to amino acids as primary sources of chiral templates. The challenge is to find innovative and stereocontrolled methods of chain extension reactions that lead to higher-carbon aminodeoxy sugars. 

Anthracyclines isolated from stieptomyces show a 2,3,6-trideoxy-3-amino-L-/yxo-configurated sugar oc-attached to the aglycon. Therefore, the first interest centered on the synthesis of aminodeoxy sugars in the l-lyxo series, e.g., daunosamine [46-50]. Several new glycosides were prepared [51] in order to evaluate structure-activity relationships. 

Pelyvas IF, Monneret C, Herczegh P (1988) Synthetic Aspects of Aminodeoxy Sugar of Antibiotics. Springer, Berlin Heidelberg New York... 

The separation of aminodeoxy sugars from neutral and acidic sugars may be readily achieved using an acetate buffer at pH 5 (the iV-acetyl derivatives of D-glucosamine and n-galactosamine have characteristic Mg values in borate buffer at pH 10). M. C. Foster and Ashton have found zone electrophoresis to be useful in the separation of streptomycin components. They observed the following mobilities X 10 ) streptomycin, 22.5 mannosidostreptomycin, 19.5 streptothricin, 24.0 streptidine, 24.9 and streptamine, 6.3. 

Pelyvas, 1. F. Monneret, C. Herczegh, P. Synthetic aspects of aminodeoxy sugars of antibiotics., Springer-Verlag Berlin, 1988,244pp. 

The action of ammonia or amines on the epoxy sugars results in ring opening with the formation of aminodeoxy sugars or their derivatives. An interesting example is found in the conversion of D-xylose to 3-amino-3-deoxy-D-ribose, a structural component of the antibiotic puromycin (80). The transformation (see formulas on p. 392) is remarkable in that derivatives of all four D-aldopentoses are involved. 

Hirama has reviewed the application of intramolecular conjugate additions of y- and fi-carbamoyloxy-a,j8-unsaturated esters fc.f , Vol.21, p.89) in the synthesis of a variety of aminodeoxy-sugars." Further anomalously coupled nucleosides, e.a.. isonucleosides (46), have been obtained by Michael-type addition of purines to unsaturated aldehydes (Scheme 13). complex amino-disaccharides have been synthesized by employing the cycloadducts... 

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