title: Difluorocarbene-Derived Trifluoromethylthiolation and [(18)F]Trifluoromethylthiolation of Aliphatic Electrophiles.
abstract: 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.
authors.affiliation: Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (China).
authors.forename: Jian
authors.initials: J
authors.lastname: Zheng
authors.affiliation: Division of Nuclear Medicine and Molecular Imaging, Massachusetts General Hospital & Department of Radiology, Harvard Medical School, 55 Fruit St., White 427, Boston, MA (USA).
authors.forename: Lu
authors.initials: L
authors.lastname: Wang
authors.affiliation: Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (China).
authors.forename: Jin-Hong
authors.initials: JH
authors.lastname: Lin
authors.affiliation: Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032 (China). jchxiao@sioc.ac.cn.
authors.forename: Ji-Chang
authors.initials: JC
authors.lastname: Xiao
authors.affiliation: Division of Nuclear Medicine and Molecular Imaging, Massachusetts General Hospital & Department of Radiology, Harvard Medical School, 55 Fruit St., White 427, Boston, MA (USA). liang.steven@mgh.harvard.edu.
authors.forename: Steven H
authors.initials: SH
authors.lastname: Liang
mesh_terms: D005461:Fluorine / Q000737:chemistry; D005462:Fluorine Radioisotopes / Q000737:chemistry; D006845:Hydrocarbons, Fluorinated / Q000138:chemical synthesis* / Q000737:chemistry; D007477:Ions / Q000737:chemistry; D015394:Molecular Structure; D013438:Sulfhydryl Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D013455:Sulfur / Q000737:chemistry
chemical_list: D005462:Fluorine Radioisotopes; D006845:Hydrocarbons, Fluorinated; D007477:Ions; D013438:Sulfhydryl Compounds; C121084:difluorocarbene; D005461:Fluorine; D013455:Sulfur
keywords: carbenes; fluorine; isotopic labeling; positron emission tomography; sulfur