The Dimethylmaleoyl Group as Amino Protective Group – Application to the Synthesis of Glucosamine-Containing Oligosaccharides

Abstract

Glucosamine was readily transformed into N-dimethylmaleoyl (DMM) protected derivative 1 which furnished trichloroacetimidate 4 as glycosyl donor. Reaction with various acceptors (5a–g) in the presence of TMSOTf as the catalyst afforded the corresponding β-glycosides 6a–g generally in high yields. Cleavage of the DMM group was readily accomplished by treatment with aqueous NaOH and then with HCl (pH 5). Starting from 1 also DMM group containing glycosyl acceptors 9 and 14a–c were synthesized. They furnished with trichloroacetimidates 12 and 4 as glycosyl donors β(1-4)- and β(1-3)-linked disaccharides 13 and 15a–c, respectively. From 18 as galactosyl donor and 14a as acceptor β(1-3)-linked disaccharide 19 was obtained in high yield, which is a versatile building block for the important Galβ(1-3)GlcNAc unit. 19 was transformed into trichloroacetimidate 21; glycosylation with 5e as acceptor gave trisaccharide 22 which furnished on partial deprotection Galβ(1-3)GlcNAcβ(1-4)Glc derivative 24. Thus, the wide applicability of DMM as amino protective group in oligosaccharide synthesis is exhibited.