Institute of Organic Chemistry, Leibniz University Hannover, Schneiderberg 1B, D-30167 Hannover, Germany.
Magn Reson Chem. 2011 Jun;49(6):328-42. doi: 10.1002/mrc.2751. Epub 2011 Mar 31.
Three different kinds of substituted chiral adamantane molecules-adamantanones, dioxolanoadamantanes and dithiolano-adamantanes-were studied in the dirhodium experiment (NMR measurement with 1:1 molar mixtures with Rh((II))(2)(R)-(+)-MTPA in CDCl(3)). Their different behavior in adduct formation is described, and the possibility of determining enantiomeric purities and absolute configurations is explored. Detailed inspection of one- and two-dimensional NMR experiments allowed for an interpretation of steric and electronic intra-adduct interaction showing that the phenyl groups of Rh* tend to enwrap the bound adamantane ligand so that through-space effects over a range of 6-7 Å away from the binding rhodium atom can be observed. Even slight differences in the relative orientation of phenyl groups can be monitored when comparing diastereomeric adducts via NMR signal dispersion.
三种不同取代手性金刚烷分子——金刚烷酮、二氧戊环金刚烷和二硫戊环金刚烷——在双铑实验中进行了研究（用 1:1 摩尔比的 Rh((II))(2)(R)-(+)-MTPA与 CDCl(3)中的金刚烷混合物进行 NMR 测量）。描述了它们在加合物形成中的不同行为，并探讨了确定对映体纯度和绝对构型的可能性。对一维和二维 NMR 实验的详细检查允许对内加合物相互作用的立体和电子进行解释，表明 Rh*的苯基基团倾向于包裹结合的金刚烷配体，从而可以观察到距离结合铑原子 6-7Å 范围内的空间效应。通过 NMR 信号色散比较非对映异构体加合物时，甚至可以监测苯基基团相对取向的微小差异。
