Diversification of Amidyl Radical Intermediates Derived from C-H Aminopyridylation

TheN-activating substituents typically encountered in C-H amination chemistry are challenging to remove and havelimited scope for synthetic elaboration. Here, we demonstrate thatN-benzylaminopyridinium species provide a platform forsynthetic elaboration via reductive N-N bond activation to unveil electrophilicN-centered radicals. These reactive intermediatescan be trapped either via anti-Markovnikov olefin carboamination to provide access to tetrahydroisoquinolines or via aza-Rubottomchemistry with silyl enol ethers to provide alpha-amino ketones

Automated summary

The study demonstrates that N-benzylaminopyridinium species can provide a platform for synthetic elaboration through reductive N-N bond activation, resulting in the formation of electrophilic N-centered radicals. These reactive intermediates can be further transformed into tetrahydroisoquinolines and alpha-amino ketones via different reactions.