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Article

A Simple Model System for the Study of Carbohydrate−Aromatic Interactions

Supporting Info

Giancarlo Terraneo,^† Donatella Potenza,^† Angeles Canales,^‡ Jesus Jiménez-Barbero,*^‡ Kim K. Baldridge,*^§ and Anna Bernardi*^†; ;

Contribution from the Universita' di Milano, Dipartimento di Chimica Organica e Industriale e Centro di Eccellenza CISI, via Venezian 21, 20133 Milano, Italy, Centro de Investigaciones Biolgicas, Consejo Superior de Investigaciones Cientficas, Ramiro de Maeztu 9, 28040 Madrid, Spain, and Institute of Organic Chemistry, University of Zrich, Winterthurerstrasse 190, CH-8057 Zrich, Switzerland

J. Am. Chem. Soc., 2007, 129 (10), pp 2890–2900

DOI: 10.1021/ja066633g

Publication Date (Web): February 20, 2007

†

Universita' di Milano.

‡

Consejo Superior de Investigaciones Científicas.

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

University of Zürich.

, anna.bernardi@unimi.it, ; , jjbarbero@cib.csic.es, ; , kimb@oci.unizh.ch

Abstract

A molecular scaffold was identified which enables the establishment of intramolecular interactions between a monosaccharide and a nearby phenyl ring. A group of molecules containing four different monosaccharides (glucose, galactose, N-acetyl-glucosamine, and N-acetyl-galactosamine) was synthesized and used to investigate the extent and nature of this carbohydrate−arene interaction, as well as the effect on the overall 3D structure of the molecules involved. The sugar−aromatic distance was evaluated by rigorous NMR studies supported by molecular modeling and found to be constant throughout the series, independent of the nature of the sugar and of the conformational behavior of the fragment connecting the two elements. Ab initio calculations at the B3LYP/DZV(2d,p) level of theory enable the analysis of the electronic nature of the interaction. The study shows that, given the opportunity, persistent intramolecular aromatic−sugar interactions can be established and can significantly influence overall molecular shape and energetics. These results have important implications in the design of structural mimics of oligosaccharides.

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