Native Amide‐Directed C(sp³)−H Amidation Enabled by Electron‐Deficient Rh^III Catalyst and Electron‐Deficient 2‐Pyridone Ligand

Abstract

Trivalent group‐9 metal catalysts with a cyclopentadienyl‐type ligand (CpMIII; M=Co, Rh, Ir, Cp=cyclopentadienyl) have been widely used for directed C−H functionalizations, albeit that their application to challenging C(sp3)−H functionalizations suffers from the limitations of the available directing groups. In this report, we describe directed C(sp3)−H amidation reactions of simple amide substrates with a variety of substituents. The combination of an electron‐deficient CpERh catalyst (CpE=1,3‐bis(ethoxycarbonyl)‐substituted Cp) and an electron‐deficient 2‐pyridone ligand is essential for high reactivity.