Photochemical Regioselective C(sp³)–H Amination of Amides Using <i>N</i>-Haloimides

Abstract

A metal-free regioselective C(sp³)-H amination of amides using <i>N</i>-haloimides in the presence of lithium <i>tert</i>-butoxide and visible light is presented herein. This photoexcited approach is straightforward, and it aminates a wide variety of amides under mild conditions without the use of photocatalysts, external radical initiators, or oxidants. A halogen-bonded intermediate between the <i>tert</i>-butoxide base and the <i>N</i>-haloimide is proposed to be responsible for the increased photoreactivity. Calculations show that the formation of this electron donor-acceptor complex presents an exergonic energy profile.