title: Design and synthesis of a new type of ferrocene-based planar chiral DMAP analogues. A new catalyst system for asymmetric nucleophilic catalysis.
abstract: A new first-generation catalyst system for nucleophilic catalysis has been developed. It is based on a planar chiral ferrocene skeleton with either the potent nucleophile 4-(dimethylamino)pyridine (DMAP) or the related 4-nitropyridine N-oxide attached in either the 2- or the 3-position. The syntheses are short, efficient, and enantioselective and X-ray crystal structures of both DMAP-derived catalysts are presented. The DMAP-based catalysts were tested in asymmetric reactions and the 3-derivative 14 showed good activity and a moderate level of enantioselectivity. The sense of induction (selectivity) was studied using molecular modeling and the results pointed at new directions for future generations of catalysts based on this design.
authors.affiliation: Department of Chemistry, Technical University of Denmark, Buildings 201 and 206, DK-2800 Kgs. Lyngby, Denmark.
authors.forename: Jimmi Gerner
authors.initials: JG
authors.lastname: Seitzberg
authors.forename: Carsten
authors.initials: C
authors.lastname: Dissing
authors.forename: Inger
authors.initials: I
authors.lastname: Søtofte
authors.forename: Per-Ola
authors.initials: PO
authors.lastname: Norrby
authors.forename: Mogens
authors.initials: M
authors.lastname: Johannsen
mesh_terms: D015761:4-Aminopyridine / Q000031:analogs & derivatives* / Q000737:chemistry; D002384:Catalysis; D005296:Ferrous Compounds / Q000737:chemistry*; D000075163:Metallocenes; D008958:Models, Molecular; D015394:Molecular Structure; D013237:Stereoisomerism
chemical_list: D005296:Ferrous Compounds; D000075163:Metallocenes; D015761:4-Aminopyridine; C003885:4-dimethylaminopyridine; C004998:ferrocene