Iron‐catalyzed C‐7 selective NH2 amination of indoles

Abstract

7‐Aminoindoles are important synthetic intermediates to a broad range of bioactive molecules. Transition metal‐catalyzed directed C–H amination is among the most straightforward route for their synthesis, whereas methods that could directly incorporate an NH2 group in a highly selective manner remains elusive. Moreover, there is still high demand for the development of earth‐abundant metal catalysis for such attractive reactivity. We present here the first C‐7 selective NH2 amination of indoles through a directed homolytic aromatic substitution (HAS) with iron‐aminyl radical. The reaction exhibits broad substrate scope, tolerates variety of functional groups, and is readily scalable with catalyst loading down to 0.1 mol% and turnover number (TON) up to 4500.