Nickel-catalyzed umpolung C -S radical reductive cross coupling of S -(trifluoromethyl)arylsulfonothioates with alkyl halides

作者：Yang, Yu-Zhong; Lv, Gui-Fen; Hu, Ming; Li, Yang^*; Li, Jin-Heng^*

来源：CHINESE CHEMICAL LETTERS, 2023, 34(11): 108590.

DOI：10.1016/j.cclet.2023.108590

• Nickel
• Radical
• Reductive cross coupling
• S -(Trifluoromethyl)arylsulfonothioates
• Alkyl halides
• Alkyl aryl thioethers

A new cooperative nickel reductive catalysis and N,N-dimethylformamide-mediated strategy for umpol-ung C -S radical reductive cross coupling of S-(trifluoromethyl)arylsulfonothioates with alkyl halides to produce alkyl aryl thioethers is described. This reaction features excellent selectivity, wide functional-ity tolerance, broad substrate scope, and facile late-stage modification of biologically relevant molecules. Mechanistic studies recognize initial generation of an amidyl radical anion via thermoinduced reduction of DMF with Sn, followed by umpolung reduction and single electron transfer of the nucleophilic sulfonyl moiety to form a sulphydryl radical and engage the Ni0/NiI/Ni III/NiI catalytic cycle.& COPY; 2023 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.

• 单位
  南昌航空大学; y; 兰州大学