Aminodeoxy sugars synthesis

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... 

Amino sugars are components of antibiotic substances109 and bacterial polysaccharides,1,0 and are therefore of interest. The nucleoside antibiotics amicetin, bamicetin, and plicacetin contain, as the sugar residue, a monoaminopentadeoxy disaccharide that is closely related to maltose. In view of the reported antibiotic and antitumor properties of these pyrimidine nucleosides,111,112 the synthesis of aminodeoxy derivatives of maltose would be of interest. 

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. 

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. 

A. Rosenthal and G. Schollnhammer, New route to branched-chain aminodeoxy sugars by reaction of ketoses with acetonitrile. Synthesis of methyl 3-C-2 -aminocthyl-2-dcoxy- -D-araWrco-hexopyranoside, Can. J. Chem., 52 (1974) 51-54. 

Hanessian, S, Plessas, N R, Reaction of 0-benzylidene sugars with A-bromosuccinimide. HI. Applications to the synthesis of aminodeoxy and deoxy sugars of biological importance, J. Org. Chem., 34, 1045-1053, 1969. 

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