Erosion of Stereochemical Control with Increasing Nucleophilicity: O-Glycosylation at the Diffusion Limit

• Published in: Journal of organic chemistry Vol. 75; no. 4; pp. 1107 - 1118
• Main Authors: Beaver, Matthew G, Woerpel, K. A
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 19.02.2010; Amer Chemical Soc
• Subjects: Carbohydrates with 4, 5, 6, ... C atoms, dissacharides and oligosaccharides; Carbohydrates. Nucleosides and nucleotides; Chemical reactivity; Chemistry; Chemistry, Organic; Diffusion; Exact sciences and technology; Glycosides - chemistry; Glycosylation; Glyoxylates - chemistry; Kinetics; Kinetics and mechanisms; Molecular Structure; Organic chemistry; Oxygen - chemistry; Physical Sciences; Preparations and properties; Reactivity and mechanisms; Science & Technology; Stereoisomerism; 4,6-O-BENZYLIDENE-DIRECTED BETA-MANNOPYRANOSYLATION; SOLUTION-PHASE; OLIGOSACCHARIDE SYNTHESIS; DIRECT CONSTRUCTION; 2'-CARBOXYBENZYL GLYCOSIDES; DONORS; CONFORMATIONAL-ANALYSIS; STEREOSELECTIVE-SYNTHESIS; OXOCARBENIUM IONS; AQUEOUS-SOLUTION; Kinetic control; Nucleophilic reaction; Ethanol; Oside; Glycosylation; Stereochemistry; Experimental study; Reaction rate; Chemical substitution; Stereoselectivity; Carbenium compounds; Glycoside; SN1 mechanism; Chemical reactivity; Nucleophilic substitution; Nucleophilicity; Nucleophilic addition; Nucleophile

Nucleophilic substitution reactions of 2-deoxyglycosyl donors indicated that the reactivity of the oxygen nucleophile has a significant impact on stereoselectivity. Employing ethanol as the nucleophile resulted in a 1:1 (α:β) ratio of diastereomers under SN1-like reaction conditions. Stereoselective...