非对映异构二核苷甲基膦酸酯：用二维核磁共振ROESY技术确定构型
Diastereomeric dinucleoside-methylphosphonates: determination of configuration with the 2-D NMR ROESY technique.
作者信息
Löschner T, Engels J W
机构信息
Institut für Organische Chemie, Frankfurt am Main, FRG.
出版信息
Nucleic Acids Res. 1990 Sep 11;18(17):5083-8. doi: 10.1093/nar/18.17.5083.
Abstract
The determination of configuration at phosphorus in diastereomeric dinucleoside-methylphosphonates having the -O-P(= O)(-CH3)-O- internucleotide linkage with the NOE derived ROESY NMR technique is described for ApT, TpT, ApA, TpA and CpG. For this purpose ROE's from the P-CH3 group to the protons in the nearest neighbourhood were measured. These ROE's are different within diastereomeric pairs of a dimer enabling us to deduce the individual configuration. The validity of the method is proven in comparison with dimers of known configuration (ApT, TpT). Together with a recently published diastereoselective synthesis method a more homogeneous picture between physical properties and the corresponding configuration is provided. There is an improvement in our knowledge about the stereochemistry of these substances which could not be deduced from the data known before.
摘要
描述了采用基于NOE的ROESY NMR技术，对具有-O-P(=O)(-CH₃)-O-核苷酸间连接的非对映异构二核苷甲基膦酸酯中磷原子的构型进行测定，涉及ApT、TpT、ApA、TpA和CpG。为此，测量了从P-CH₃基团到最近邻质子的ROE。这些ROE在二聚体的非对映异构体对中是不同的，这使我们能够推断出各自的构型。与已知构型的二聚体（ApT、TpT）相比，证明了该方法的有效性。结合最近发表的非对映选择性合成方法，提供了物理性质与相应构型之间更一致的情况。我们对这些物质立体化学的认识有了改进，这是根据以前已知的数据无法推断出来的。
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