Ito Yuta, Touyama Akihiro, Uku Minako, Egami Hiromichi, Hamashima Yoshitaka
School of Pharmaceutical Sciences, University of Shizuoka.
Chem Pharm Bull (Tokyo). 2019;67(9):1015-1018. doi: 10.1248/cpb.c19-00352.
Thiocyanation of aromatic compounds has been investigated using the combination of 1-chloro-1,2-benziodoxol-3-(1H)-one (1) and (trimethylsilyl)isothiocyanate (TMSNCS). The reaction with electron rich aromatic compounds proceeded smoothly to provide the thiocyanated products in high yield, while electron deficient heteroaromatic compounds were not suitable for this reaction. In these reactions, the regioselectivity was generally high. Transformations of the products were also investigated to demonstrate the utility of the reaction. Based on NMR experiments, we propose that thiocyanogen chloride is generated in situ as an active species.
利用1-氯-1,2-苯并碘氧杂环戊-3-(1H)-酮(1)和(三甲基甲硅烷基)异硫氰酸酯(TMSNCS)的组合，对芳香族化合物的硫氰化反应进行了研究。与富电子芳香族化合物的反应顺利进行，以高产率得到硫氰化产物，而缺电子杂芳香族化合物不适合该反应。在这些反应中，区域选择性一般较高。还对产物的转化进行了研究，以证明该反应的实用性。基于核磁共振实验，我们提出原位生成的氯化硫氰作为活性物种。
