Unprecedented chiral molecular recognition in a C3-symmetric environment.
The enantiomeric recognition of alpha-chiral primary ammonium ions has been studied with benzene-based tripodal tris(oxazoline) receptors. Contrary to the literature and our expectation, a good level of chiral discrimination is observed with one of the tripodal receptors, which provides a C3-symmetric chiral environment on guest binding. The chiral discrimination has been found to be general in the case of alpha-aryl substituted guests, suggesting pi-pi interactions as an important factor. This result raises a question with respect to the origin of the chiral discrimination since little steric or electronic difference is expected between the diastereomeric inclusion complexes. Binding studies by NMR titration and isothermal titration calorimetry show that the chiral discrimination results from the different thermodynamic stabilities between the diastereomeric complexes and that the host-guest complex formation is driven by favorable enthalpy changes with a minor negative contribution by entropy changes. The X-ray crystal structures for both of the diastereomeric inclusion complexes are resolved, which unambiguously show the binding mode and provide clues on the origin of the chiral discrimination. Bond angle analyses indicate that the minor complex experiences a larger steric strain, which is discernible when it is viewed from "three-body" interactions between the host and the guest. The guest and oxazoline phenyl rings are well stacked, indicating interplay of the pi-pi interactions. The pi-pi interactions are believed to stabilize host-guest complexes, thereby endowing the highly flexible receptors with a substantial enantio-discrimination.
Kim
Sung-Gon
SG
Department of Chemistry, Center for Integrated Molecular Systems, Division of Molecular and Life Science, Pohang University of Science and Technology, San 31 Hyoja-dong, Pohang 790-784, Republic of Korea.
Kim
Kyung-Hyun
KH
Jung
Junyang
J
Shin
Seung Koo
SK
Ahn
Kyo Han
KH
D018360:Crystallography, X-Ray; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D010456:Peptides, Cyclic / Q000737:chemistry*; D000644:Quaternary Ammonium Compounds / Q000737:chemistry*; D011956:Receptors, Cell Surface / Q000737:chemistry*; D013237:Stereoisomerism; D013379:Substrate Specificity
D010456:Peptides, Cyclic; D000644:Quaternary Ammonium Compounds; D011956:Receptors, Cell Surface; C074972:westiellamide