Amine α-heteroarylation via photoredox catalysis: a homolytic aromatic substitution pathway.

The direct α-heteroarylation of tertiary amines has been accomplished via photoredox catalysis to generate valuable benzylic amine pharmacophores. A variety of five-and six-membered chloroheteroarenes are shown to function as viable coupling partners for the α-arylation of a diverse range of cyclic and acyclic amines. Evidence is provided for a homolytic aromatic substitution mechanism, in which a catalyticallygenerated α-amino radical undergoes direct addition to an electrophilic chloroarene.