Native Amide-Directed C(sp 3 )-H Amidation Enabled by Electron-Deficient Rh III Catalyst and Electron-Deficient 2-Pyridone Ligand.

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