Streptomycin mercaptolysis

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. 

Kuehl, Flynn, Brink and Folkers38 in 1946 showed that mercaptolysis of streptomycin leads to the formation of an ethyl thiostreptobios-aminide diethyl thioacetal hydrochloride (XXX). The same substance... 

Wolfrom and coworkers had found that the mercaptolysis of the crystalline calcium chloride double salt of streptomycin trihydrochloride yielded, after chromatographic purification, two anomeric forms of ethyl tetraacetylthiostreptobiosaminide diethyl mercaptal. Mercaptolysis of dihydrostreptomycin yielded an amorphous ethyl dihydrothio-streptobiosaminide hydrochloride which formed crystalline N-acetyl and pentaacetyl derivatives. The ability of the ring in this latter compound to resist hydrolysis and to form a thioglycoside instead of a thio-... 

There thus remain only two possible structures for streptomycin, XXXIX and XL. Either of these possible structures could account for all data so far accumulated, since these data rest upon hydrolytic (meth-anolysis or mercaptolysis) operations which could involve a change in the... 

Both methanolysis and mercaptolysis of streptomycin B yielded known derivatives of streptidine, streptobiosamine and D-mannose, while dihydrostreptomycin B yielded derivatives of streptidine, dihydro-streptobiosamine and D-mannose.The derivatives of D-mannose which were obtained are listed in Table II. These results, together with the analytical data for the hydrochloride and reineckate of streptomycin B, established the composition of the free base as C27H490nN7 and showed that the substance exists as glycosidically linked streptidine,... 

---