Elucidating heteroatom influence on homonuclear 4 J(H,H) coupling constants by DFT/NMR approach
© 2019 John Wiley & Sons, Ltd.
| Veröffentlicht in: | Magnetic resonance in chemistry : MRC. - 1985. - 58(2020), 6 vom: 02. Juni, Seite 566-575 |
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| 1. Verfasser: | |
| Weitere Verfasser: | , , , |
| Format: | Online-Aufsatz |
| Sprache: | English |
| Veröffentlicht: |
2020
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| Zugriff auf das übergeordnete Werk: | Magnetic resonance in chemistry : MRC |
| Schlagworte: | Journal Article Research Support, Non-U.S. Gov't 1H conformational analysis density function theory heteroatoms long-range coupling constant nuclear magnetic resonance organic synthesis |
| Zusammenfassung: | © 2019 John Wiley & Sons, Ltd. We report the structural dependency of long range scalar J-coupling constant across four bonds as function of the dihedral angles Φ1 and Φ3. The calculated homonuclear coupling constants 4 J(H,H ), obtained at a density functional theory level, were measured between C(1)─X(2) and X(2)─C(3) bonds in three-term models, where C, N, O, and S were systematically used as the second atom of the alkyl structures (1-4). The 4 J(H,H) calculated values, tabulated for variation of 30° for both Φ1 and Φ3, have disclosed an unexpected detectable coupling constant (4 J(H,H ) ≥ 1 Hz) across heteroatoms, useful to provide valuable structural information. A 2-methyl-1,3-dithiane sulfide (5) was used as a case study to prove the applicability and reliability of the calculated values to real issues. The 4 J(H,H ) values obtained at density functional theory for the system 4 have reproduced with good accuracy an unexpected experimental 4 J(H2ax-H4ax ) = 1.01 Hz of sulfide molecule (5), suggesting these calculated coupling constant values as a new powerful tool for the organic synthesis and stereochemical analysis |
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| Beschreibung: | Date Completed 24.05.2021 Date Revised 24.05.2021 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
| ISSN: | 1097-458X |
| DOI: | 10.1002/mrc.4983 |