Synthesis of Sterically Congested Carbamates of Carbohydrates through Organic Base Catalysis

Abstract

4,6-O-Benzylidene acetal protected α-methoxy d-glucose and d-glucosamine are useful building blocks for the syntheses of carbohydrate derivatives and functional molecular assemblies. In this research, we have developed a general method for the preparation of C-3 carbamate derivatives of densely functionalized glucose and glucosamine with isocyanates using organic bases as catalysts. Without a suitable catalyst, the C-3 hydroxy group of the glucosamine derivative could not be converted into the corresponding carbamates when treated with isocyanates. Several organic bases were screened as the catalysts for the reactions, and we discovered that 5.0 mol% of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) was an effective catalyst for the carbamoylation reaction. A library of both alkyl and aryl carbamate derivatives of the two sterically congested carbohydrates have been effectively synthesized using the current method.