Direct sp3 C–H bond activation adjacent to nitrogen in heterocycles

Abstract

Activation of sp³ C–H bonds adjacent to nitrogen in heterocycles is an attractive transformation that is emerging as a practical method in organic synthesis. This tutorial review aims to summarize the key examples of direct functionalization of nitrogen-containing heterocycles via metal-mediated and metal-catalyzed processes, which is meant to serve as a foundation for future investigations into this rapidly developing area of research. The review covers functionalization of N-heterocycles via α-lithiation with alkyllithium/diamine complexes, α-amino radical formation, metal-catalyzed direct C–H activation, C–H oxidations and oxidative couplings, and metal-catalyzed carbene insertions.