Diastereo‐ and Enantioselective Construction of Vicinal All‐Carbon Quaternary Stereocenters via Iridium/Europium Bimetallic Catalysis

Abstract The diastereo‐ and enantioselective construction of vicinal all‐carbon quaternary stereocenters is a formidable task. We here report a synergistic bimetallic catalysis via a chiral N,N′ ‐dioxide‐europium (Eu) complex and a phosphoramidite‐iridium (Ir) catalyst for the asymmetric allylation of oxindole derivatives by using challenging trisubstituted allylic esters. The allylated products bearing vicinal all‐carbon quaternary stereocenters were obtained with good diastereoselectivities (up to 20 : 1 dr) and excellent enantioselectivities (up to 99 % ee). Control experiments showed that the complementary diastereomers of the products were not accessible by the change of the stereochemistry of the chiral N,N′ ‐dioxide ligand.