Enantioselective Oxidative Gold Catalysis Enabled by a Designed Chiral P,N-Bidentate Ligand

A newly developed P,N-bidentate ligand enables enantioselective intramolecular cyclopropanation by a reactive -oxo gold carbene intermediate generated in situ. The ligand design is based on our previously proposed structure (with a well-organized triscoordinated gold center) of the carbene intermediate in the presence of a P,N-bidentate ligand. A C-2-symmetric piperidine ring was incorporated in the ligand as the nitrogen-containing moiety. A range of racemic transformations of -oxo gold carbene intermediates have been developed recently, and this new class of chiral ligands could enable their modification for asymmetric synthesis, as demonstrated in this study.