title: Site-selective arene C-H amination via photoredox catalysis.
abstract: Over the past several decades, organometallic cross-coupling chemistry has developed into one of the most reliable approaches to assemble complex aromatic compounds from preoxidized starting materials. More recently, transition metal-catalyzed carbon-hydrogen activation has circumvented the need for preoxidized starting materials, but this approach is limited by a lack of practical amination protocols. Here, we present a blueprint for aromatic carbon-hydrogen functionalization via photoredox catalysis and describe the utility of this strategy for arene amination. An organic photoredox-based catalyst system, consisting of an acridinium photooxidant and a nitroxyl radical, promotes site-selective amination of a variety of simple and complex aromatics with heteroaromatic azoles of interest in pharmaceutical research. We also describe the atom-economical use of ammonia to form anilines, without the need for prefunctionalization of the aromatic component.
authors.affiliation: Department of Chemistry, University of North Carolina-Chapel Hill, Chapel Hill, NC 27599-3290, USA.
authors.forename: Nathan A
authors.initials: NA
authors.lastname: Romero
authors.affiliation: Department of Chemistry, University of North Carolina-Chapel Hill, Chapel Hill, NC 27599-3290, USA.
authors.forename: Kaila A
authors.initials: KA
authors.lastname: Margrey
authors.affiliation: Department of Chemistry, University of North Carolina-Chapel Hill, Chapel Hill, NC 27599-3290, USA.
authors.forename: Nicholas E
authors.initials: NE
authors.lastname: Tay
authors.affiliation: Department of Chemistry, University of North Carolina-Chapel Hill, Chapel Hill, NC 27599-3290, USA. nicewicz@unc.edu.
authors.forename: David A
authors.initials: DA
authors.lastname: Nicewicz