Design, Synthesis, and Evaluation of Extended C4–Symmetric Dirhodium Tetracarboxylate Catalysts

The synthesis and evaluation of six C4-symmetric bowl-shaped dirhodium tetracarboxylate catalysts are described. These elaborate high-symmetry catalysts are readily generated by means of the self-assembly of four C1-symmetric ligands around the dirhodium core. These catalysts are capable of highly site-selective, diastereoselective, and enantioselective C–H functionalization reactions by means of donor/acceptor carbene-induced C–H insertions.