The stereochemical assignment of acyclic polyols: a computational study of the NMR data of a library of stereopentad sequences from polyketide natural products
The stereochemical assignment of acyclic polyols: a computational study of the NMR data of a library of stereopentad sequences from polyketide natural products
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DOI：
10.1016/j.tet.2010.06.022
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发表时间：
2010-08-14
期刊：
影响因子：
2.1
通讯作者：
Goodman, Jonathan M.
中科院分区：
文献类型：
--
作者：
Smith, Steven G.;Channon, Julia A.;Goodman, Jonathan M.
柔性分子的可靠立体化学指认是一项极具挑战性的任务。这一点从一套完整的16个非对映异构体的核磁共振化学位移中得到了说明，他们的实验数据在这里是第一次报告的。尽管实验光谱彼此非常相似，但对不同非对映异构体的位移的相似性分析表明，一些非对映异构体比其他的更具区分性。此外，还用密度泛函GIAO方法计算了这16个化合物的核磁共振位移，并用我们最近发展的CP3参数对这些分子进行了结构归属。即使在实验光谱非常相似的情况下，我们的CP3参数也可以高置信度地正确指定非对映异构体对。(C)2010爱思唯尔有限公司。保留所有权利。
The reliable stereochemical assignment of flexible molecules, such as acyclic polypropionates is an enormously challenging task. This is illustrated by the NMR chemical shifts for a complete set of sixteen diastereomeric stereopentads whose experimental data is reported here for the first time. Although the experimental spectra are very similar to each other, analysis of the similarity between the shifts of different diastereoisomers reveals that some diastereoisomers are much more distinctive than others. In addition, the NMR shifts of the sixteen compounds have also been calculated using DFT GIAO calculations, and the use of our recently developed CP3 parameter for structure assignment is illustrated for these molecules. Even in cases where the experimental spectra are very similar, our CP3 parameter makes possible the correct assignment of pairs of diastereoisomers with high confidence. (C) 2010 Elsevier Ltd. All rights reserved.