title: Catalytic enantioselective construction of tetrasubstituted carbons by self-assembled poly rare earth metal complexes.
abstract: Rare earth metal-based enantioselective catalysts that can promote practical cyanation reactions of ketones and ketoimines were developed. These catalytic enantioselective tetrasubstituted carbon-forming reactions are useful platforms for the synthesis of biologically active compounds. ESI-MS and crystallographic studies of the asymmetric catalysts revealed that the active catalysts are polymetallic complexes produced through the assembly of modules. The higher-order structure of the polymetallic complexes has strong effects on catalyst activity and enantioselectivity. Controlling the higher-order structure of artificial polymetallic asymmetric catalysts is a new strategy for optimizing asymmetric catalysts. Recent progress in this approach is also described.
authors.affiliation: Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
authors.forename: Masakatsu
authors.initials: M
authors.lastname: Shibasaki
authors.forename: Motomu
authors.initials: M
authors.lastname: Kanai
mesh_terms: D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D003486:Cyanides / Q000737:chemistry; D007659:Ketones / Q000737:chemistry; D008674:Metals, Rare Earth / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D003486:Cyanides; D007659:Ketones; D008674:Metals, Rare Earth; D002244:Carbon