Zheng Jian, Wang Lu, Lin Jin-Hong, Xiao Ji-Chang, Liang Steven H
Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (China).
Division of Nuclear Medicine and Molecular Imaging, Massachusetts General Hospital & Department of Radiology, Harvard Medical School, 55 Fruit St., White 427, Boston, MA (USA).
Angew Chem Int Ed Engl. 2015 Nov 2;54(45):13236-40. doi: 10.1002/anie.201505446. Epub 2015 Sep 21.
The first trifluoromethylthiolation and [(18)F]trifluoromethylthiolation of alkyl electrophiles with in situ generated difluorocarbene in the presence of elemental sulfur and external (radioactive) fluoride ion is described. This transition-metal-free approach is high yielding, compatible with a variety of functional groups, and operated under mild reaction conditions. The conceptual advantage of this exogenous-fluoride-mediated transformation enables unprecedented syntheses of [(18)F]CF3S-labeled molecules from most commonly used [(18)F]fluoride ions. The rapid radiochemical reaction time (≤1 min) and high functional-group tolerance allow access to a variety of aliphatic [(18)F]CF3S compounds in high yields.
本文描述了在元素硫和外部(放射性)氟离子存在下,利用原位生成的二氟卡宾对烷基亲电试剂进行首次三氟甲硫基化反应以及[(18)F]三氟甲硫基化反应。这种无过渡金属的方法产率高,与多种官能团兼容,且在温和的反应条件下进行。这种外源性氟介导的转化的概念优势使得能够从最常用的[(18)F]氟离子出发,以前所未有的方式合成[(18)F]CF3S标记的分子。快速的放射化学反应时间(≤1分钟)和高官能团耐受性使得能够高产率地获得各种脂肪族[(18)F]CF3S化合物。