Insulin-like, and insulin-antagonistic, carbohydrate derivatives. The synthesis of aryl and aralkyl D-mannopyranosides and 1-thio-D-mannopyranosides.

A number of novel, aryl and aralkyl D-mannopyranosides and 1-thio-D-mannopyranosides were synthesized for evaluation of insulin-like and insulin-antagonistic properties. The substituted-phenyl alpha-D-mannopyranosides were prepared by the general procedure of Helferich and Schmitz-Hillebrecht, the substituted-phenyl 1-thio-alpha-D-mannopyranosides by a method corresponding to the Michael synthesis of aromatic glycosides, and the aralkyl 1-thio-alpha-D-mannopyranosides by aralkylation of 2,3,4,6-tetra-O-acetyl-1-thio-alpha-D-mannopyranose (15) and subsequent O-deacetylation. Compound 15 was obtained by basic cleavage of the amidino group in 2-S-(tetra-O-acetyl-alpha-D-mannopyranosyl)-2-thiopseudourea hydrobromide, the product of the reaction of tetra-O-acetyl-alpha-D-mannosyl bromide with thiourea. Benzyl 1-thio-beta-D-mannopyranoside, obtained by reaction of the sodium salt of 1-thio-beta-D-mannopyranose with alpha-bromotoluene, and benzyl 1-thio-alpha-L-mannopyranoside were also synthesized, in order to assess the stereospecificity of the biological activities measured.