期刊論文
| 學年 | 102 |
|---|---|
| 學期 | 2 |
| 出版（發表）日期 | 2014-06-01 |
| 作品名稱 | Theoretical investigation of conformational stabilities and 13C NMR chemical shifts of a seven-membered ring thiosugar, (3R,4R,5R,7S)-7-(hydroxymethyl)thiepane-3,4,5-triol |
| 作品名稱（其他語言） | |
| 著者 | Tai, Chin-Kuen; Yeh, Pao-Ling; Wu, Yun-Sheng; Shih, Tzenge-Lien; Wang, Bo-Cheng |
| 單位 | 淡江大學化學學系 |
| 出版者 | Amsterdam: Elsevier BV |
| 著錄名稱、卷期、頁數 | Journal of Molecular Structure 1068, pp.84-93 |
| 摘要 | DFT/B3LYP/6-311++G(d,p) calculations have been performed to obtain optimized structures for fourteen conformers of (3R,4R,5R,7S)-7-(hydroxymethyl)thiepane-3,4,5-triol. These conformers are considered as the twist-chair (TC) and twist-boat (TB) conformations. Among all conformers, the TCS5 and TCS6 conformers appear to be the most energetically stable since they contain an intramolecular hydrogen bond between hydroxyl group at C(8) and S atom. Boltzmann weighting factor analysis provides valuable information on the population of the fourteen conformers, including both the TC and TB conformations. The analysis results demonstrate that the TCS2, TCS5, and TCS6 conformers provide a major population contribution with Boltzamann weighting factors larger than 7% as compared to other conformers. For these conformers of (3R,4R,5R,7S)-7-(hydroxymethyl)thiepane-3,4,5-triol, the GIAO/HF, GIAO/DFT/OPBE, GIAO/DFT/B3LYP and GIAO/DFT/mPW1PW91 calculations with the 6-311++G(d,p), 6-311+G(2d,p), cc-pVDZ and cc-pVTZ basis sets were used to obtain their 13C NMR chemical shifts. The calculated 13C NMR chemical shifts of the TCS2, TCS5, and TCS6 conformers show a close correlation with experimental data, within 2.4–3.0 ppm of MAE values. The experimental 13C NMR chemical shifts represent a combination of contributions from all the conformers. In our investigation, the calculated 13C NMR chemical shifts of the mixture of (3R,4R,5R,7S)-7-(hydroxymethyl)thiepane-3,4,5-triol conformers display a remarkable MAE and RMS improvement comparing to those for each individual conformer. The most appropriate calculation method and basis set to evaluate the theoretical 13C NMR chemical shifts for these conformers are OPBE/6-311+G(2d,p). Calculated results represent that the conformation of (3R,4R,5R,7S)-7-(hydroxymethyl)thiepane-3,4,5-triol can be determined by the intramolecular hydrogen bond which could be simulated by the 13C NMR chemical shift calculation. |
| 關鍵字 | |
| 語言 | en_US |
| ISSN | 0022-2860 |
| 期刊性質 | 國外 |
| 收錄於 | SCI |
| 產學合作 | |
| 通訊作者 | Shih, Tzenge-Lien; Wang, Bo-Cheng |
| 審稿制度 | 是 |
| 國別 | NLD |
| 公開徵稿 | |
| 出版型式 | 紙本 |
| 相關連結 |
機構典藏連結 ( http://tkuir.lib.tku.edu.tw:8080/dspace/handle/987654321/97928 ) |