Metal-Containing Schiff Base/Sulfoxide Ligands for Pd(II)-Catalyzed Asymmetric Allylic C-H Aminations

Metal-containing Schiff base/sulfoxides were developed as chiral ligands for Pd(II)-catalyzed asymmetric intramolecular allylic C-H amination reactions. The use of metal-containing Schiff base ligands allows tuning the selectivity and reactivity of the Pd(II)-catalyst, whereby a Schiff base-Cu(II)/sulfoxide ligand in combination with Pd(OAc)(2) showed the best performance. Both internal and terminal alkenes were applicable, and the C-H amination products were obtained in up to 91:9 er

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(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 (CpRh)-Rh-E catalyst (Cp-E=1,3-bis(ethoxycarbonyl)-substituted Cp) and an electron-deficient 2-pyridone ligand is essential for high reactivity