Title

Binuclear copper(II) complexes discriminating epimeric glycosides and α- and β-glycosidic bonds in aqueous solution

Document Type

Article

Publication Date

2016

Keywords

Catalysis, Glycosides, Selective hydrolysis, Binuclear copper(II) complexes, Chiral

Abstract

Two chiral binuclear copper(II) complexes were synthesized and characterized for the first time as efficient chemoselective catalysts for the hydrolysis of aryl glycosides and disaccharides in aqueous solution at near neutral pH. Under these conditions, discrimination of epimeric aryl α-glycopyranosides was observed by both 29-fold different reaction rates and 3-fold different proficiency of the catalyst. Additionally, large differentiation of the nature of α- and β-glycosidic bond in aryl glycosides as model compounds is apparent, but also noted in selected disaccharides. The influence of the chirality of the complexes and the role of the configuration of the carbohydrate upon interaction with the catalyst is discussed in detail. Lastly, a putative mechanism for the metal complex-catalyzed hydrolysis is derived from the experimental evidence pointing at deprotonation of the hydroxyl group at C-2 as a pre-requisite for glycoside hydrolysis.

Comments

Support by the National Science Foundation (CHE-1305543) and the Arkansas Biosciences Institute to S.S. is gratefully acknowledged. The facilities used in this study were supported by the National Institute of General Medical Sciences(NIGMS) of the National Institutes of Health (NIH) by Grant number P30 GM103450.

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