Ruthenium‐Catalyzed meta‐Selective C−H Mono‐ and Difluoromethylation of Arenes through ortho‐Metalation Strategy

作者: Zhong-Yuan Li , Liang Li , Qi-Li Li , Kun Jing , Hui Xu

DOI: 10.1002/CHEM.201700354

关键词: Organic chemistrySubstrate (chemistry)CatalysisRutheniumSurface modificationChemistryMetalationFunctional groupPalladiumCombinatorial chemistryCatalytic cycle

摘要: The first example for the ruthenium-catalyzed ligand-directed meta-selective C-H mono- and difluoromethylation is developed, affording a variety of new meta-mono- difluoromethylated 2-phenylpyridines, 2-phenylpyrimidines, 1-phenylpyrazoles in moderate-to-good yields. This transformation exhibits broad substrate scope, good functional group tolerance, high efficiency, offers practical approach to synthesize arenes. Mechanistic studies indicate that reaction pathway involving palladium-initiated radical species involved catalytic cycle. dual system consisting compatible ruthenium(II) palladium(0) complexes enables key processes activation mono-/difluoromethyl-radical formation occur achieves functionalization efficiently. In addition, present protocol can also be extended non-fluoromethylation.

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