title: Amide-directed photoredox-catalysed C-C bond formation at unactivated sp3C-H bonds.
abstract: 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. 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 sp3C-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.
authors.affiliation: Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, USA.
authors.forename: John C K
authors.initials: JC
authors.lastname: Chu
authors.affiliation: Department of Chemistry, Colorado State University, Fort Collins, Colorado 80523, USA.|Department of Chemistry, Columbia University, New York, New York 10027, USA.
authors.forename: Tomislav
authors.initials: T
authors.lastname: Rovis
mesh_terms: D000577:Amides / Q000737:chemistry*; D002244:Carbon / Q000737:chemistry*; D002384:Catalysis / Q000528:radiation effects; D060326:Chemistry Techniques, Synthetic; D006859:Hydrogen / Q000737:chemistry*; D006860:Hydrogen Bonding / Q000528:radiation effects; D009584:Nitrogen / Q000737:chemistry; D010084:Oxidation-Reduction / Q000528:radiation effects
chemical_list: D000577:Amides; D002244:Carbon; D006859:Hydrogen; D009584:Nitrogen