Photoinduced α‐Aminoalkylation of Sulfonylarenes with Alkylamines

α‐Aminoalkylation of sulfonylarenes with alkylamines was found to be induced by photoirradiation. Here various types of alkylamines, such as trialkylamines, dialkylamines, N,N‐dialkylanilines and N‐alkylanilines as well as sulfonylarenes containing an azole, azine, heterole or benzene ring are available. The reaction proceeds through a homolytic aromatic substitution (HAS) process consisting of addition of an α‐aminoalkyl radical to a sulfonylarene and elimination of the sulfonyl radical to give the α‐arylalkylamine, where photoirradiation is considered to induce homolysis of sulfonylarenes leading to the generation of α‐aminoalkyl radicals that make a radical chain operative. α‐Aminoalkylation of sulfonylarenes with alkylamines was found to proceed successfully in the presence of a base in MeOH under photoirradiation, giving a wide variety of α‐arylalkylamines. The reaction is initiated by photolysis of the S−Ar bond of sulfonylarenes leading to generation of α‐aminoalkyl radicals, which get into a radical chain to give α‐arylalkylamines.