title: Catalytic olefin hydroamination with aminium radical cations: a photoredox method for direct C-N bond formation.
abstract: While olefin amination with aminium radical cations is a classical method for C-N bond formation, catalytic variants that utilize simple 2° amine precursors remain largely undeveloped. Herein we report a new visible-light photoredox protocol for the intramolecular anti-Markovnikov hydroamination of aryl olefins that proceeds through catalytically generated aminium radical intermediates. Mechanistic studies are consistent with a process involving amine oxidation via electron transfer, turnover-limiting C-N bond formation, and a second electron transfer step to reduce a carbon-centered radical, rendering the overall process redox-neutral. A range of structurally diverse N-aryl heterocycles can be prepared in good to excellent yields under conditions significantly milder than those required by conventional aminium-based protocols.
authors.affiliation: Department of Chemistry, Princeton University , Princeton, New Jersey 08544, United States.
authors.forename: Andrew J
authors.initials: AJ
authors.lastname: Musacchio
authors.forename: Lucas Q
authors.initials: LQ
authors.lastname: Nguyen
authors.forename: G Hudson
authors.initials: GH
authors.lastname: Beard
authors.forename: Robert R
authors.initials: RR
authors.lastname: Knowles