通过对红黄素裂解产物3-甲磺酸基-5-甲基巯基苯酚CD谱的比较测定红黄素的绝对构型。

Enantiomer Pub Date : 2002-03-01 DOI:10.1080/10242430212197
G. Raabe, Charlotte Repges, Yuekui Wang, J. Fleischhauer
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引用次数: 2

摘要

通过比较其热分解产物3-甲磺酸基-5-甲基巯基苯酚的CD谱,间接确定了红黄素的绝对构型。在HF/6-31+G*水平上进行几何优化,我们发现3-甲磺酸基-5-甲基巯基苯酚的(R)-异构体有15个局部最小值。然后,用非经验CIS方法计算每个结构的玻尔兹曼加权光谱的叠加得到化合物的CD谱。利用从头算理论在ZPE + MP2/6-31+G*//HF/6-31+G*能级上确定的这些最小值的相对能量,计算了相应的玻尔兹曼因子。通过比较观察到的和计算得到的最长波长棉花效应的标志,我们给出了热解产物的绝对构型。由于进一步的计算表明,在热解条件下,红黄素及其分解产物中的三配位硫原子的构型是稳定的,因此我们得出结论,红黄素相应的硫原子的绝对构型是相同的。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Determination of the absolute configuration of rubroflavin by comparison of measured and calculated CD spectra of its thermolysis product 3-methanesulfinyl-5-methylmercaptophenol.
The absolute configuration of rubroflavin has been determined indirectly by comparison of the measured and the calculated CD spectrum of its thermal decomposition product 3-methanesulfinyl-5-methylmercaptophenol. Performing geometry optimizations at the HF/6-31+G* level we found fifteen local minima for the (R)-isomer of 3-methanesulfinyl-5-methylmercaptophenol. The CD spectrum of the compound was then obtained as a superposition of the Boltzmann-weighted spectra for each structure calculated with the non-empirical CIS method. The corresponding Boltzmann factors have been calculated employing the relative energies of these minima determined at the ZPE + MP2/6-31+G*//HF/6-31+G* level of ab initio theory. Comparing the signs of the observed and calculated longest wave length Cotton effect we assign an absolute configuration to the thermolysis product. Since additional calculations revealed that the tricoordinate sulfur atom in rubroflavin and in its decomposition product is configurationally stable under the conditions of thermolysis we conclude that the absolute configuation at the corresponding sulfur atom of rubroflavin is the same.
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