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-alpha-D-glucopyranosyl bromide in the presence of a mixed catalyst, Hg(CN)2 and HgBr2, in benzene-nitromethane. Reaction occurred on the alpha, beta-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.
Tobari
A
A
Faculty of Pharmaceutical Sciences, Josai University, Sakado, Saitama, Japan.
Shimizu
T
T
Miyamae
H
H
Nagasawa
A
A
Kawase
M
M
Saito
S
S
D001965:Bromides / Q000737:chemistry*; D002384:Catalysis; D003486:Cyanides / Q000737:chemistry*; D006031:Glycosylation; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D017669:Mercury Compounds / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D011522:Protons; D013739:Testosterone / Q000031:analogs & derivatives* / Q000737:chemistry
C115972:17-O-acetyltestosterone; D001965:Bromides; D003486:Cyanides; D017669:Mercury Compounds; D011522:Protons; D013739:Testosterone; C042720:mercuric bromide; C040189:mercuric cyanide