Department of Chemical Science and Engineering, Kobe University, 1-1 Rokkodai, Nada, Kobe, 657-8501, Japan.
Sci Rep. 2018 Jan 26;8(1):1704. doi: 10.1038/s41598-018-19878-x.
The chirality of winding vine-shaped heterobiaryls with molecular asymmetry is recognized by a sugar-based chiral oxidant. Kinetic resolution of (±)-bisbenzoimidazole bearing an olefin moiety takes place with Shi's asymmetric epoxidation to observe k value up to ca. 35 affording the corresponding epoxide. The reaction of a (±)-bithiophene derivative also recognized the chirality to give the corresponding epoxide with er of 96:4 at 39% conversion. Dynamic kinetic resolution is found to take place when unsymmetrical biaryl composed of benzoimidazole/thiophene is subjected to Shi's epoxidation, whose conversion of the racemic substrate exceeds to 50%.
手性糖基手性氧化剂可识别具有分子不对称性的扭曲藤状杂双芳烃的手性。（±）-双苯并咪唑带有烯烃部分的动力学拆分通过 Shi 的不对称环氧化反应进行，观察到 k 值高达约 35，得到相应的环氧化物。（±）-联噻吩衍生物的反应也识别出手性，在 39%转化率下得到相应的环氧化物，ee 值为 96:4。当由苯并咪唑/噻吩组成的不对称双芳基经受 Shi 的环氧化时，发现发生动态动力学拆分，其外消旋底物的转化率超过 50%。
