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Aggregation of a Tetrasaccharide Acceptor Observed by NMR: Synthesis of Pentasaccharide Fragments of the LeaLex Tumor-Associated Hexasaccharide Antigen

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Title: Aggregation of a Tetrasaccharide Acceptor Observed by NMR: Synthesis of Pentasaccharide Fragments of the LeaLex Tumor-Associated Hexasaccharide Antigen
Author: Kuir, Deng; Guillemineau, Mickaël; Auzanneau, France-Isabelle
Abstract: We report the synthesis of a tetrasaccharide and two pentasaccharide fragments of the LeaLex tumor associated carbohydrate antigen α-L-Fuc-(1→4)-[β-D-Gal-(1→3)]-β-D-GlcNAc-(1→3)-β-D-Gal-(1→4)-[α-L-Fuc-(1→3)]-β-D-GlcNAc-(1→OR). The choice of protecting groups permitted a one-step global deprotection (Na/NH3(l)). The protected chlorohexyl glycoside pentasaccharide was the precursor to the hexyl glycoside, to be used as a soluble inhibitor, and the aminohexyl glycoside analogue, to be conjugated to proteins for surface immobilization and immunization experiments. We observed that a linear tetrasaccharide that contained two N-acetylglucosamine residues and a free OH group gave two distinct sets of 1H NMR signals when the data was acquired in deuterated chloroform. Data acquisition at variable concentrations and variable temperatures suggest that the second set of NMR signals results from aggregation of the tetrasaccharide driven by the formation of intermolecular H-bonds involving the NHAc. While the formation of intra- and intermolecular H-bonds involving N¬-acetylgucosamine residues has been reported in non-H-bonding solvents, this is, to our knowledge, the first time that these lead to the appearance of two distinct sets of signals in the NMR spectra. This aggregation, may explain the lack of reactivity observed when attempting to glycosylate such acceptor using non H-bonding solvents such as dichloromethane.
URI: http://hdl.handle.net/10214/8911
Date: 2015-04-10
Citation: Kuir, D.; Guillemineau, M.; Auzanneau, F. I.; J. Org. Chem. 2015, 80, 5004−5013. DOI: 10.1021/acs.joc.5b00405


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