Muta Ryuhei, Torigoe Takeru, Kuninobu Yoichiro
Department of Molecular and Material Sciences, Interdisciplinary Graduate School of Engineering Sciences , Kyushu University , 6-1 Kasugakoen , Kasuga-shi , Fukuoka 816-8580 , Japan.
Institute for Materials Chemistry and Engineering , Kyushu University , 6-1 Kasugakoen , Kasuga-shi , Fukuoka 816-8580 , Japan.
Org Lett. 2019 Jun 7;21(11):4289-4292. doi: 10.1021/acs.orglett.9b01474. Epub 2019 May 16.
The regioselective C-H trifluoromethylthiolation of six-membered heteroaromatic compounds via nucleophilic attack of a CFS source on the electrophilically activated six-membered heteroaromatic ring was developed. The reaction proceeds in good yield with good functional group tolerance, even on a gram-scale. The key to the successful regioselective transformation is the presence of an additive (2,4-dinitrobenzenesulfonyl chloride). The regioselective trifluoromethylthiolation of quinidine derivative is also demonstrated. Trifluoromethylthiolation, followed by S-oxidation, affords the corresponding sulfones.
通过CFS源对亲电活化的六元杂芳环进行亲核进攻，实现了六元杂芳族化合物的区域选择性C-H三氟甲硫基化反应。该反应产率良好，官能团耐受性好，甚至可放大至克级规模。成功实现区域选择性转化的关键在于添加剂（2,4-二硝基苯磺酰氯）的存在。还展示了奎尼丁衍生物的区域选择性三氟甲硫基化反应。三氟甲硫基化后进行S-氧化，可得到相应的砜。
