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

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. Direct C(sp3)−H functionalization reactions of native amides can facilitate streamlined synthesis of valuable molecules, but their insufficient directing ability is one of the current severe challenges of the field. Here we report that the combination of an electron‐deficient RhIII catalyst and an electron‐deficient 2‐pyridone ligand shows high catalytic activity for C(sp3)−H amidation of various native amides.