Structure determination of slowly exchanging conformers in solution using high‐resolution NMR,computational modeling and DFT‐GIAO chemical shielding: application to an erythronolide A derivative |
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Authors: | Dieter Muri Clémence Corminboeuf Erick M Carreira Damien Jeannerat |
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Institution: | 1. Laboratorium für Organische Chemie, ETH‐Zürich, CH‐8093 Zürich, Switzerland;2. Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), CH‐1015 Lausanne, Switzerland;3. Départment de Chimie Organique et de Chimie Physique, Université de Genève, 30 Quai E. Ansermet, CH‐1211 Genève, Switzerland |
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Abstract: | We discuss and demonstrate the potential of HSQC‐TOCSY and HSQC‐NOESY experiments to offer solutions for overlap problems in COSY and NOESY spectra, leading to improved signals that can be unambiguously assigned to individual carbons. Direct comparison of experimental 1H and 13C chemical shielding with density functional theory (DFT)‐calculated values are uninformative; in contrast, the relative differences in experimental shielding between pairs of molecules correlates well with the relative differences in DFT‐GIAO shielding for the computed lowest energy conformers. A detailed application of both experimental and theoretical techniques is illustrated for slowly exchanging conformers of an erythronolide A derivative, which demonstrates that structure determination can strongly benefit from the interplay between experiment and theory. Copyright © 2009 John Wiley & Sons, Ltd. |
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Keywords: | structure determination conformers NMR erythronolide synthesis spectral aliasing |
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