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NMR and Computational Investigations of the Chiral Discrimination Processes Involving a Cyclic Tetraamidic Chiral Selector
Author(s) -
UccelloBarretta Gloria,
Balzano Federica,
Martinelli Jonathan,
Gasparrini Francesco,
Pierini Marco,
Villani Claudio
Publication year - 2011
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201100408
Subject(s) - chemistry , steric effects , molecular model , enantiomer , hydrogen bond , intermolecular force , molecular mechanics , stereochemistry , amide , nuclear magnetic resonance spectroscopy , molecular recognition , computational chemistry , docking (animal) , molecular dynamics , molecule , organic chemistry , medicine , nursing
The chiral recognition mechanism of a macrocyclic tetraamidic receptor for the enantiomers of N ‐(3,5‐dinitrobenzoyl)valine‐ N ‐hexylamide has been investigated in detail through a combination of NMR spectroscopy and molecular modeling studies. Intra‐ and intermolecular ROE effects provided information on the conformations of the free and complexed partners, and also on their relative arrangement in solution during complexation. Molecular mechanics calculations and molecular docking studies gave results in agreement with the spectroscopic data, correctly reproducing the relative stability of the two diastereoisomeric complexes. A stereochemical model for the complexed species is presented in which hydrogen‐bonding interactions between amide fragments drive the association process, and the enantioselectivity is modulated by aromatic–aromatic interactions and steric hindrance.