Nakakoshi Masamichi, Ueda Masafumi, Sakurai Satoshi, Miyata Okiko, Sugiura Makiko, Naito Takeaki
Chemical Analysis Center, Yokohama National University, 79-5 Tokiwadai, Hodogaya-ku, Yokohama, 240-8501, Japan.
Magn Reson Chem. 2006 Aug;44(8):807-12. doi: 10.1002/mrc.1847.
The structures of the components in the triethylborane-mediated radical addition reaction of oxime ether were investigated by 1H- and 3D-DOSY NMR methods. It has been impossible to physically separate the unstable intermediates; therefore, the structures were thus far unidentified. It has been possible to elucidate the structures of these unstable intermediates using Diffusion-Ordered Spectroscopy (DOSY) methods for the reaction in an NMR tube. The DOSY methods resolved the spectra of each starting compound, intermediate and product having different diffusion coefficients. The structure of the intermediate was shown to be due to the bonding of diethylborane to the nitrogen atom of the alkoxyamino group.
采用¹H-和3D-DOSY NMR方法研究了肟醚在三乙基硼介导的自由基加成反应中各组分的结构。由于无法物理分离不稳定的中间体，因此这些中间体的结构至今尚未确定。利用核磁共振管中反应的扩散排序光谱法（DOSY），已能够阐明这些不稳定中间体的结构。DOSY方法解析了具有不同扩散系数的每种起始化合物、中间体和产物的光谱。结果表明，中间体的结构是由于二乙基硼与烷氧基氨基的氮原子键合所致。
