Long-Range Residual Dipolar Couplings: A Tool for Determining the Configuration of Small Molecules
Long-Range Residual Dipolar Couplings: A Tool for Determining the Configuration of Small Molecules
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DOI：
10.1002/anie.201504432
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发表时间：
2015-10-19
影响因子：
16.6
通讯作者：
Griesinger, Christian
中科院分区：
文献类型：
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作者：
Nath, Nilamoni;d'Auvergne, Edward J.;Griesinger, Christian
与 NOE 和 J 耦合一起，单键残余偶极耦合 (RDC) 报告分子框架中核间矢量的三维方向，在通过 NMR 光谱对溶液中小分子的构象和构型分析中发挥着重要作用。当分子的 C-H 键很少，或者平行键太多时，可用的 RDC 可能不足以获得用于结构阐明的对齐张量。通过多个键连接原子核的长程 RDC 通常不与单键平行，因此与单键 RDC 互补。在此，我们提出了一种提取所选质子或质子组到所有远程连接的碳原子（包括非质子化碳原子）的长程 RDC 的方法。直接拟合到总长程耦合 (T=J+D) 的对准张量可以直接分析士的宁的长程和单键 RDC。
Together with NOE and J coupling, one-bond residual dipolar coupling (RDC), which reports on the three-dimensional orientation of an internuclear vector in the molecular frame, plays an important role in the conformation and configuration analysis of small molecules in solution by NMR spectroscopy. When the molecule has few C-H bonds, or too many bonds are in parallel, the available RDCs may not be sufficient to obtain the alignment tensor used for structure elucidation. Long-range RDCs that connect nuclei over multiple bonds are normally not parallel to the single bonds and therefore complement one-bond RDCs. Herein we present a method for extracting the long-range RDC of a chosen proton or group of protons to all remotely connected carbon atoms, including non-protonated carbon atoms. Alignment tensors fitted directly to the total long-range couplings (T=J+D) enabled straightforward analysis of both the long-range and one-bond RDCs for strychnine.