Cyanoglycosylation products of 17-O-acetyl-testosterone

17-O-Acetyl testosterone, which has no susceptible hydroxyl or carboxyl group for glycosylation, was glycosylated with 2,3,4,6-tetra-O-acetyl-α--glucopyranosyl bromide in the presence of a mixed catalyst, Hg(CN)₂ and HgBr₂, in benzene–nitromethane. Reaction occurred on the α,β-unsaturated ketone on the six–membered A-ring to give six 3-O-glycosides, each bearing a cyano group at the 3- or 5-position of the aglycon, and a 3-O-glycoside bearing a CONH₂ group at the 3-position. Structural analyses of these products were carried out by various NMR (¹H, ¹³C NMR, ¹H–¹H and ¹H–¹³C COSY, HMBC, and DEPT), FABMS and X-ray analyses. The mechanisms of the formations of the products are discussed. It was determined that mercuric cyanide was essential as a catalyst for the progress of the cyanoglycosylation.