Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis , Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences , 345 Lingling Road , Shanghai 200032 , P. R. China.
AnHui Province Key Laboratory of Chemistry for Inorganic/Organic Hybrid Functionalized Materials , Anhui University , Hefei , Anhui 230601 , P. R. China.
J Am Chem Soc. 2018 May 16;140(19):6169-6175. doi: 10.1021/jacs.8b03077. Epub 2018 May 7.
The copper-assisted radical carbofluorination of unactivated alkenes with fluoride ions is described. With [Cu(L3)F]HO (L3 = 4,4'-di(methoxycarbonyl)-2,2'-bipyridine) as the fluorine source and [Ag(DMPhen)(MeCN)]BF (DMPhen = 2,9-dimethyl-1,10-phenanthroline) as the chloride scavenger, the reaction of unactivated alkenes with CCl in acetonitrile provided the corresponding carbofluorination products in satisfactory yields. The protocol exhibited a wide functional group compatibility and broad substrate scope and could be extended to the use of a variety of activated alkyl chlorides other than CCl. A copper-catalyzed fluorotrifluoromethylation of unactivated alkenes was then successfully developed with CsF as the fluorine source and Umemoto's reagent as the trifluoromethylating agent. A mechanism involving the fluorine atom transfer from Cu(II)-F complexes to alkyl radicals is proposed.
描述了铜辅助的未活化烯烃与氟离子的自由基碳氟化反应。以[Cu(L3)F]HO（L3=4,4'-二甲氧基羰基-2,2'-联吡啶）为氟源，[Ag(DMPhen)(MeCN)]BF（DMPhen=2,9-二甲基-1,10-菲咯啉）为氯清除剂，未活化烯烃与 CCl 在乙腈中的反应以令人满意的收率提供了相应的碳氟化产物。该方案表现出广泛的官能团相容性和广泛的底物范围，并可扩展到使用除 CCl 以外的各种活化的烷基氯化物。然后，成功地以 CsF 为氟源、Umemoto 的试剂为三氟甲基化试剂开发了铜催化的未活化烯烃的氟三氟甲基化反应。提出了一种涉及 Cu(II)-F 配合物向烷基自由基的氟原子转移的机制。
