Enantioselective Synthesis of Ferrocene 1,3-Derivatives via Palladium/Norbornene Cooperative Catalysis

Abstract

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