Amide-directed photoredox-catalysed C-C bond formation at unactivated sp(3) C-H bonds

Article

关键词: COUPLED ELECTRON-TRANSFER;    ALPHA-AMINO-ACIDS;    FUNCTIONALIZATION;    RADICALS;    PYRROLIDINES;    OLEFINATION;    ACTIVATION;    GENERATION;    ARYLATION;    OXIDATION;   

DOI  :  10.1038/nature19810

来源: SCIE

【 摘 要 】

Carbon-carbon (C-C) bond formation is paramount in the synthesis of biologically relevant molecules, modern synthetic materials and commodity chemicals such as fuels and lubricants. Traditionally, the presence of a functional group is required at the site of C-C bond formation. Strategies that allow C-C bond formation at inert carbon-hydrogen (C-H) bonds enable access to molecules that would otherwise be inaccessible and the development of more efficient syntheses of complex molecules(1,2). Here we report a method for the formation of C-C bonds by directed cleavage of traditionally non-reactive C-H bonds and their subsequent coupling with readily available alkenes. Our methodology allows for amide-directed selective C-C bond formation at unactivated sp(3) C-H bonds in molecules that contain many such bonds that are seemingly indistinguishable. Selectivity arises through a relayed photoredox-catalysed oxidation of a nitrogen-hydrogen bond. We anticipate that our findings will serve as a starting point for functionalization at inert C-H bonds through a strategy involving hydrogen-atom transfer.

【 授权许可】

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