10583-63-8Relevant academic research and scientific papers
Why Is Direct Glycosylation with N-Acetylglucosamine Donors Such a Poor Reaction and What Can Be Done about It?
Marqvorsen, Mikkel H. S.,Pedersen, Martin J.,Rasmussen, Michelle R.,Kristensen, Steffan K.,Dahl-Lassen, Rasmus,Jensen, Henrik H.
supporting information, p. 143 - 156 (2017/04/26)
The monosaccharide N-acetyl-d-glucosamine (GlcNAc) is an abundant building block in naturally occurring oligosaccharides, but its incorporation by chemical glycosylation is challenging since direct reactions are low yielding. This issue, generally agreed upon to be caused by an intermediate 1,2-oxazoline, is often bypassed by introducing extra synthetic steps to avoid the presence of the NHAc functional group during glycosylation. The present paper describes new fundamental mechanistic insights into the inherent challenges of performing direct glycosylation with GlcNAc. These results show that controlling the balance of oxazoline formation and glycosylation is key to achieving acceptable chemical yields. By applying this line of reasoning to direct glycosylation with a traditional thioglycoside donor of GlcNAc, which otherwise affords poor glycosylation yields, one may obtain useful glycosylation results.
Protected glycosides and disaccharides of 2-amino-2-deoxy-D-glucopyranose by ferric chloride-catalyzed coupling.
Kiso,Anderson
, p. 309 - 323 (2007/10/02)
The ferric chloride-catalyzed glycosylation of hydroxy compounds by protected 2-acylamino-2-deoxy-beta-D-glucopyranose 1-acetates is described. In addition to known glycosides from the reaction of alcohols with 2-acetamido-1,3,4,6-tetra-O-acetyl-2-deoxy-beta-D-glucopyranose (3), ally (and other alkyl) beta-glycosides were obtained from the N-benzoyl, N-phenoxyacetyl, N-methoxyacetyl, N-chloroacetyl, and N-phthaloyl congeners of 3. The latter compounds, except for the N-phthaloyl derivative, gave oxazolines in the absence of an alcoholic reactant. Compound 3 and the related N-benzoyl, N-chloroacetyl, N-acetyl-3,4,6-tri-O-benzyl, and N-acetyl-4-O-acetyl-3,6-di-O-benzyl derivatives were coupled to one or more protected sugars to form protected, beta-linked disaccharides. Coupling at the 6-positions of acceptors proceeded smoothly and gave 67-80% yields. For successful coupling at positions 3 and 4, long reaction times and multiple additions of glycosyl donor were required, and yields ranged from 60% to as low as 30%. 1,3,4,6-Tetra-O-acetyl-2-(chloroacetamido)-2-deoxy-beta-D- glucopyranose appeared to be the most reactive glycosyl donor in this series. The reaction of 2-methyl-(3,4,6-tri-O-acetyl-1,2-dideoxy-alpha-D-glucopyrano)[2,1- d]-2-oxazoline (derived from 3) with allyl alcohol was catalyzed by ferric chloride, and oxazolines were detected as intermediates in some of the glycosylations of protected sugars.
