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Chiral Diaminopyrrolic Receptors for Selective Recognition of Mannosides, Part 2: A 3D View of the Recognition Modes by X‐ray, NMR Spectroscopy, and Molecular Modeling
Author(s) -
Ardá Ana,
Cañada F. Javier,
Nativi Cristina,
Francesconi Oscar,
Gabrielli Gabriele,
Ienco Andrea,
JiménezBarbero Jesús,
Roelens Stefano
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201002872
Subject(s) - molecular recognition , chemistry , hydrogen bond , molecule , intermolecular force , molecular model , stereochemistry , nuclear magnetic resonance spectroscopy , receptor , affinities , solvent , proton nmr , crystallography , organic chemistry , biochemistry
The structural features of a representative set of five complexes of octyl α‐ and β‐mannosides with some members of a new generation of chiral tripodal diaminopyrrolic receptors, namely, ( R ) ‐5 and ( S ) ‐ and ( R ) ‐7 , have been investigated in solution and in the solid state by a combined X‐ray, NMR spectroscopy, and molecular modeling approach. In the solid state, the binding arms of the free receptors 7 delimit a cleft in which two solvent molecules are hydrogen bonded to the pyrrolic groups and to the benzenic scaffold. In a polar solvent (CD 3 CN), chemical shift and intermolecular NOE data, assisted by molecular modeling calculations, ascertained the binding modes of the interaction between the receptor and the glycoside for these complexes. Although a single binding mode was found to adequately describe the complex of the acyclic receptor 5 with the α‐mannoside, for the complexes of the cyclic receptors 7 two different binding modes were required to simultaneously fit all the experimental data. In all cases, extensive binding through hydrogen bonding and CH–π interactions is responsible for the affinities measured in the same solvent. Furthermore, the binding modes closely account for the recognition preferences observed toward the anomeric glycosides and for the peculiar enantiodiscrimination properties exhibited by the chiral receptors.