CH amination reactions provide streamlined access to nitrogen-containing small molecules. Here, we disclose benzylic CH amination with N-aminopyridiniums, which are bifunctional reagents that provide avenues for further diversification. Reductive activation of the incipient NN bonds unveils electrophilic N-centered radicals, which can be engaged by nucleophilic partners such as olefins, silyl enol ethers, and electron-rich heterocycles. We highlight the synthetic potential of these sequences in the synthesis of tetrahydroisoquinolines, which are important heterocycles in molecular therapeutics, via anti-Markovnikov olefin carboamination. Unlike many CH amination reactions that provide access to protected amines, the current method installs an easily diversifiable synthetic handle that serves as a lynchpin for CH amination, deaminative NN functionalization sequences.
