While olefin amination with aminium radical cations is a classical method for C-N bond formation, catalytic variants that utilize simple secondary 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 yield under conditions significantly milder than those required by conventional aminium-based protocols.

Catalytic olefin hydroamination with aminium radical cations: A photoredox method for direct C-N bond formation

249th National Meeting (2015)

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