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. 2022 Mar 17;13(14):4122-4130.
doi: 10.1039/d2sc00222a. eCollection 2022 Apr 6.

Protecting group free glycosylation: one-pot stereocontrolled access to 1,2- trans glycosides and (1→6)-linked disaccharides of 2-acetamido sugars

Xin Qiu  1 , Anna L Garden  2   3 , Antony J Fairbanks  1   4
Affiliations

Protecting group free glycosylation: one-pot stereocontrolled access to 1,2- trans glycosides and (1→6)-linked disaccharides of 2-acetamido sugars

Xin Qiu et al. Chem Sci. .

Abstract

Unprotected 2-acetamido sugars may be directly converted into their oxazolines using 2-chloro-1,3-dimethylimidazolinium chloride (DMC), and a suitable base, in aqueous solution. Freeze drying and acid catalysed reaction with an alcohol as solvent produces the corresponding 1,2-trans-glycosides in good yield. Alternatively, dissolution in an aprotic solvent system and acidic activation in the presence of an excess of an unprotected glycoside as a glycosyl acceptor, results in the stereoselective formation of the corresponding 1,2-trans linked disaccharides without any protecting group manipulations. Reactions using aryl glycosides as acceptors are completely regioselective, producing only the (1→6)-linked disaccharides.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Scheme 1
Scheme 1. Unexpected disaccharide formation during attempted conversion of GlcNAc oxazoline 1a into its β-DNP glucoside 1b.
Fig. 1
Fig. 1. Composite structures of low energy conformations of glycosyl acceptors; (a) OPh glycoside 3k; (b) SPh glycoside 3l; (c) OMe glycoside 3m.
See this image and copyright information in PMC

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