Photocatalytic para-Selective C-H Functionalization of Anilines with Diazomalonates

Visible-light-induced para-selective C-H functionalization of anilines over N-H insertion was developed using diazomalonates with the help of an Ir(III) photocatalyst. The para-selective radical-radical cross coupling proceeded via C-centered radical intermediates generated from both anilines and diazomalonates. The photochemistry of anilines could be extended to other N-heterocycles, such as indole and carbazole. The reaction pathway for the selective C-C coupling was validated by electrochemical and photophysical experiments as well as computational studies.

Automated summary

Visible-light-induced para-selective C-H functionalization of anilines through N-H insertion was achieved using diazomalonates with the assistance of an Ir(III) photocatalyst. The para-selective radical-radical cross coupling occurred through C-centered radical intermediates generated from both anilines and diazomalonates. This reaction could also be extended to other N-heterocycles such as indole and carbazole, and its reaction pathway was validated through electrochemical and photophysical experiments as well as computational studies.