3. Catalytic Olefin Hydroamination with Aminium Radical Cations: A Photoredox Method for Direct C–N Bond Formation

Andrew J. Musacchio, Lucas Q. Nguyen, G. Hudson Beard, Robert R. Knowles:

https://pubs.acs.org/doi/abs/10.1021/ja5056774

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.