Streptomycin, configuration

Streptose is the first branched-chain sugar to have been identified as a component of a biological compound produced by a microorganism. This dicarbonyl sugar is known only in its derivatives. The chemistry of streptose and streptomycin has been lucidly reviewed by Lemieux and Wolfrom.1 In this article, it was noted that streptose must be either 5-deoxy-3-C -formyl-L-ribose or 5-deoxy-3-C-formyl-L-lyxose. Since then, the presence of the latter configuration (XXXIV) has been definitely established by Wolfrom and DeWalt,66 who found that N-acetyltetrahydrostreptobi-... 

Reductive desulfurization with Raney nickel of the mercaptolysis products of streptomycin has supplied one of the keys to the elucidation of the structure and configuration of that antibiotic. Since the chemistry of streptomycin has recently been reviewed37 the reactions discussed here will be considered solely as examples of hydrogenolysis and their bearing upon the problem of the structure and configuration of streptomycin will be ignored. 

It was in the famous carbohydrate group at Ohio State University that Lemieux became involved in the structural elucidation of streptomycin. He also became fascinated by the configurational correlation of sugars and amino acids, and realized that he could address this unresolved question by... 

At one time, there was much interest in using dibromotetrols for the synthesis of streptamine (107, R = H), and thence, streptomycin (151, G = guanidino). Reaction of certain dibromo tetraacetates (74 and 105) with ammonia in hot dioxane gives small yields of diaminotetrols, the configurations of which have not been fully established, but the products differ from natural streptamine. ... 

Streptidine is a diguanidinotetrol (107, R = C(NH)NH2). The configuration of streptomycin (151) with respect to the streptidine-strepto-biosamine linkage has finally been established (see p. 62). 

The absolute configuration of the streptidine moiety was determined by Dyer and A. W. Todd by applying Reeves s copper-complexing method to N,N -diacetyl-4-deoxystreptamine, derived from streptomycin by degradation. Moreover, the same conclusion was reached by Tatsuoka and coworkers on applying the Reeves method to 2,6-di-O-methylstreptamine derived from dihydrostreptomycin this revealed that the streptobiosamine moiety is attached to C-4 in the R configuration. The absolute structure of streptomycin was confirmed by an X-ray analysis of streptomycin oxime selenate. ... 

Streptomycin is an antibiotic that is especially usefijl against penicillin-resistant bacteria. The structure of streptomycin is shown in Section 22.17. (a) Identify aU of the chirality centers in the structure of streptomycin, (b) Assign the appropriate (R) or (5) designation for the configuration of each chirality center in streptomycin. 

Streptomycin oxime selenate tetrahydrate (absolute configuration)... 

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