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 α‐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 C₂‐symmetric piperidine ring was incorporated in the ligand as the nitrogen‐containing moiety. A range of racemic transformations of α‐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.