title: Direct Acylation of C(sp(3))-H Bonds Enabled by Nickel and Photoredox Catalysis.
abstract: Using nickel and photoredox catalysis, the direct functionalization of C(sp(3))-H bonds of N-aryl amines by acyl electrophiles is described. The method affords a diverse range of α-amino ketones at room temperature and is amenable to late-stage coupling of complex and biologically relevant groups. C(sp(3))-H activation occurs by photoredox-mediated oxidation to generate α-amino radicals which are intercepted by nickel in catalytic C(sp(3))-C coupling. The merger of these two modes of catalysis leverages nickel's unique properties in alkyl cross-coupling while avoiding limitations commonly associated with transition-metal-mediated C(sp(3))-H activation, including requirements for chelating directing groups and high reaction temperatures.
authors.affiliation: Department of Chemistry, Princeton University, 120 Washington Road, Princeton, NJ, 08544, USA.
authors.forename: Candice L
authors.initials: CL
authors.lastname: Joe
authors.affiliation: Department of Chemistry, Princeton University, 120 Washington Road, Princeton, NJ, 08544, USA. agdoyle@princeton.edu.
authors.forename: Abigail G
authors.identifier: http://orcid.org/0000-0002-6641-0833
authors.initials: AG
authors.lastname: Doyle
mesh_terms: D000215:Acylation; D002384:Catalysis; D006860:Hydrogen Bonding; D009532:Nickel / Q000737:chemistry*; D010084:Oxidation-Reduction; D055668:Photochemical Processes
chemical_list: D009532:Nickel
keywords: C−H activation; acylation; cross-coupling; nickel; photochemistry