Binuclear copper(II) complexes discriminating epimeric glycosides andα- andβ-glycosidic bonds in aqueous solution.
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 arylα-glycopyranosides was observed both by 29-fold different reaction rates and 3-fold different proficiency of the catalyst. Additionally, large differentiation of the nature ofα- andβ- 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.
Department of Chemistry and Biochemistry, University of Arkansas, 345 N Campus Drive, Fayetteville, AR 72701, USA.
Susanne
S
Striegler
Department of Chemistry and Biochemistry, University of Arkansas, 345 N Campus Drive, Fayetteville, AR 72701, USA.
Qiu-Hua
QH
Fan
Department of Chemistry and Biochemistry and Center for Nanoscience, University of Missouri - St. Louis, St. Louis, MO 63121, USA.
Nigam P
NP
Rath
Catalysis; binuclear copper(II) complexes; chiral; glycosides; selective hydrolysis
Carbohydr Res. 2010 Dec 10;345(18):2596-604
21044780
Talanta. 1986 Dec;33(12):943-51
18964236
J Am Chem Soc. 2003 Sep 24;125(38):11518-24
13129353
Inorg Chem. 2010 Mar 15;49(6):2639-48
20166683
J Biol Chem. 1973 Apr 10;248(7):2487-8
4698227
J Inorg Biochem. 2015 Aug;149:25-38
25969174
Carbohydr Res. 2011 Oct 18;346(14):2075-83
21764045
Org Lett. 2003 Dec 11;5(25):4819-22
14653682
J Med Chem. 2003 Sep 11;46(19):3985-4001
12954052
J Med Chem. 2012 Apr 26;55(8):3945-59
22449031
Nat Chem Biol. 2011 Aug 21;7(10):685-91
21857660
Bioorg Med Chem. 2003 May 15;11(10):2255-61
12713835
J Org Chem. 2008 Sep 19;73(18):7181-8
18712923
Org Biomol Chem. 2006 Nov 7;4(21):3913-22
17047870
Annu Rev Biochem. 2002;71:847-85
12045113
Tetrahedron Lett. 1969 Jul;(33):2807-10
5804734
Org Biomol Chem. 2014 May 7;12(17):2792-800
24668069
Acc Chem Res. 2012 Feb 21;45(2):239-47
21967389
Carbohydr Res. 2005 Dec 12;340(17):2670-4
16216229
Carbohydr Res. 2007 Feb 26;342(3-4):467-81
17112490
Acta Crystallogr A. 2008 Jan;64(Pt 1):112-22
18156677
Carbohydr Res. 2011 May 1;346(6):733-8
21429479