Metallaphotocatalytic synthesis of anilines through tandem C-N transposition and C-H alkylation of alkylamines

Alkylamines have a range of applications including as reagents in organic synthesis and as bioactive compounds in medicinal chemistry. Methods for the synthesis of alkylamines, however, typically suffer from low availability or inaccessibility of key reaction components and uncontrollable selectivity. While photocatalytic two-component reactions have become versatile strategies for the synthesis of alkylamines, multicomponent variants remain underdeveloped. Here we describe a metallaphotoredox-promoted three-component amination reaction using tertiary alkylamines, nitroarenes and carboxylic acids to give N-alkyl aniline products. The utility of this three-component approach is highlighted through the availability and broad scope of the reaction substrates and the application to the expedited synthesis of drug molecules and intermediates. Mechanistic investigations reveal this chemo- and regioselective transformation probably proceeds through a formal amine group transposition and C-H alkylation of a tertiary alkylamine substrate. N-Alkyl amines are prevalent compounds in organic synthesis and medicinal chemistry; however, their synthesis can be impeded by the availability of key reaction components and low selectivity. Now, a metallaphotocatalytic chemo- and regioselective synthesis of N-alkyl anilines is reported that uses readily available tertiary alkylamines, nitroarenes and carboxylic acids.