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

doi:10.1016/j.molstruc.2014.03.070

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題名:	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
作者:	Tai, Chin-Kuen;Yeh, Pao-Ling;Wu, Yun-Sheng;Shih, Tzenge-Lien;Wang, Bo-Cheng
貢獻者:	淡江大學化學學系
關鍵詞:	Thiosugars;Flexible structure;DFT calculation;Boltzmann weighting factor;NMR spectroscopy;Intramolecular hydrogen bond
日期:	2014-06-25
上傳時間:	2014-05-01 14:03:25 (UTC+8)
出版者:	Amsterdam: Elsevier BV
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.
關聯:	Journal of Molecular Structure 1068, pp.84-93
DOI:	10.1016/j.molstruc.2014.03.070
顯示於類別:	[化學學系暨研究所] 期刊論文

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