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

作者：Chu, John C. K.; Rovis, Tomislav^*

来源：Nature, 2016, 539(7628): 272-275.

DOI：10.1038/nature19810

• COUPLED ELECTRON-TRANSFER
• ALPHA-AMINO-ACIDS
• FUNCTIONALIZATION
• RADICALS
• PYRROLIDINES
• OLEFINATION
• ACTIVATION
• GENERATION
• ARYLATION
• OXIDATION

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.

• 出版日期2016-11-10