Catalytic Site-Selective Carbamoylation of Pyranosides.

Abstract

Carbamate-bearing carbohydrates contribute to the pharmacological properties of various natural glycosides. The catalytic site-selective carbamoylation of minimally protected pyranosides was achieved for the first time to bypass protection/deprotection sequences. 1-Carbamoylimidazoles were used as the carbamoylation reagents to circumvent the harmful and unstable phosgene and isocyanates. This borinic acid catalyzed transformation granted an expedient access to the tumor cell-binding carbamoylmannoside moiety of bleomycins and analogs in yields of 56% to 89%.