Convenient syntheses of daunomycinone-7-D-glucuronides and doxorubicinone-7-D-glucuronides

The first synthesis of new doxorubicin and daunomycin analogs containing glucuronic acid moieties instead of daunosamine are described. The desired products, daunomycinone-7-D-glucuronide (DM7G, 10) and doxorubicinone-7-D- glucuronide (DX7G, 11) were conveniently prepared through the glycosylation at 7-hydroxyl group of daunomycinone (4) or 14-acetoxydoxorubicinone (6) with glucuronic acid derivative 7 by the Koenigs-Knorr procedure followed by alkaline deacetylatipn using aqueous LiOH solution and amberlite cation exchange material. The anomeric configuration and conformation of all products were fully characterized by assignment of ¹H NMR chemical shifts and H-H coupling constants based on reported literatures.