Enantioselective\nSynthesis of Ferrocene 1,3-Derivatives\nvia Palladium/Norbornene Cooperative Catalysis

Herein, we report a regio-and stereoselective distal\nC–H\nfunctionalization protocol for ferrocenes, leading to the synthesis\nof planar chiral ferrocene-1,3-derivatives by a Catellani-type reaction.\nThe successful Pd(II)/norbornene catalyst combination can reach the\ninaccessible reaction site of ferrocene and accomplishes the selective\nC(3)-arylation of ferrocenyl methylamine. The ligand-controlled synergistic\nPd/norbornene metal–organic cooperative catalysis under aerobic\nconditions successfully provides an array of ferrocene-1,3-derivatives\nin moderate-to-good yields with good enantio- and diastereoselectivities.\nA unique class of ferrocene 1,3-ligands, including PPFA-like and pincer\ntype ligands bearing central and planar chirality, has been successfully\nsynthesized by following this synthetic methodology.