title: Enantioselective oxidative gold catalysis enabled by a designed chiral P,N-bidentate ligand.
abstract: 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.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, Santa Barbara, CA (USA) http://www.chem.ucsb.edu/∼zhang/index.html; Current address: College of Science, Northwest A&F University, 3 Taicheng Road, Yangling 712100, Shaanxi (China).
authors.forename: Kegong
authors.initials: K
authors.lastname: Ji
authors.forename: Zhitong
authors.initials: Z
authors.lastname: Zheng
authors.forename: Zhixun
authors.initials: Z
authors.lastname: Wang
authors.forename: Liming
authors.initials: L
authors.lastname: Zhang
mesh_terms: D002384:Catalysis; D018360:Crystallography, X-Ray; D003521:Cyclopropanes / Q000737:chemistry; D006046:Gold / Q000737:chemistry*; D008024:Ligands; D008697:Methane / Q000031:analogs & derivatives / Q000737:chemistry; D008968:Molecular Conformation; D009584:Nitrogen / Q000737:chemistry; D010084:Oxidation-Reduction; D010758:Phosphorus / Q000737:chemistry; D010880:Piperidines / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D003521:Cyclopropanes; D008024:Ligands; D010880:Piperidines; C030011:carbene; D010758:Phosphorus; C032727:piperidine; D006046:Gold; C030797:cyclopropane; D009584:Nitrogen; D008697:Methane
keywords: asymmetric catalysis; carbenes; cyclopropanation; gold; oxidation