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首页> 外文期刊>Theoretical Chemistry Accounts >Determination of the absolute configuration of chiral molecules via density functional theory calculations of vibrational circular dichroism and optical rotation: The chiral alkane D3-anti-trans-anti-trans-anti-trans-perhydrotriphenylene
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Determination of the absolute configuration of chiral molecules via density functional theory calculations of vibrational circular dichroism and optical rotation: The chiral alkane D3-anti-trans-anti-trans-anti-trans-perhydrotriphenylene

机译：通过振动圆二色性和旋光性的密度泛函理论计算确定手性分子的绝对构型：手性烷烃D3 -反-反-反-反-反-反-过-全氢联苯

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摘要

The Absolute configuration (AC) of the chiral alkane D3-anti-trans-anti-trans-anti-trans-perhydrotriphenylene (PHTP), 1, is determined by comparison of density functional theory (DFT) calculations of its vibrational circular dichroism (VCD) and optical rotation (OR) to the experimental VCD and OR of (+)?1, obtained in high enantiomeric excess using chiral gas chromatography. Conformational analysis of 1 demonstrates that the all-chair (CCCC) conformation is the lowest in energy and that other conformations are too high in energy to be significantly populated at room temperature. The B3PW91/TZ2P calculated IR spectrum of the CCCC conformation of 1 is in excellent agreement with the experimental IR spectrum, confirming the conformational analysis and demonstrating the excellent accuracy of the B3PW91 functional and the TZ2P basis set. The B3PW91/TZ2P calculated VCD spectrum of the CCCC conformation of S-1 is in excellent agreement with the experimental VCD spectrum of (+)?1, unambiguously defining the AC of 1 to be S(+)/R(?). The B3LYP/aug-cc-pVDZ calculated OR of S-1 over the range 589–365 nm has the same sign and dispersion as the experimental OR of (+)?1, further supporting the AC S(+)/R(?). Our results confirm the AC proposed earlier by Farina and Audisio. This study provides a further demonstration of the excellent accuracy of VCD spectra predicted using Stephens’ equation for vibrational rotational strengths together with the ab initio DFT methodology, and further documents the utility of VCD spectroscopy in determining the ACs of chiral molecules.
机译：通过比较振动反应的密度泛函理论（DFT）计算确定了手性烷烃D3 -反-反-反-反-反-反-过-全氢联苯（PHTP）1的绝对构型（AC）圆二色性（VCD）和旋光性（OR）对实验VCD和（+）？1的OR，是使用手性气相色谱法以高对映体过量获得的。 1的构象分析表明，全椅子（CCCC）构象的能量最低，而其他构象的能量太高，无法在室温下显着分布。 B3PW91 / TZ2P计算得出的CCCC构型1的IR光谱与实验IR光谱非常吻合，证实了构象分析，并证明了B3PW91功能和TZ2P基集的出色准确性。 B-3PW91 / TZ2P计算得出的S-1的CCCC构象的VCD光谱与（+）？1的实验VCD光谱非常吻合，明确地将1的AC定义为S（+）/ R（？）。 B3LYP / aug-cc-pVDZ计算得出的S-1在589–365 nm范围内的OR与（+）？1的实验OR具有相同的符号和色散，进一步支持了AC S（+）/ R（？ ）。我们的结果证实了Farina和Audisio早些时候提出的AC。这项研究进一步证明了使用斯蒂芬斯方程对振动旋转强度以及从头算DFT方法预测的VCD光谱的出色准确性，并进一步证明了VCD光谱在确定手性分子AC方面的实用性。

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