Design and synthesis of a new type of ferrocene-based planar chiral DMAP analogues. A new catalyst system for asymmetric nucleophilic catalysis.
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.
Seitzberg
Jimmi Gerner
JG
Department of Chemistry, Technical University of Denmark, Buildings 201 and 206, DK-2800 Kgs. Lyngby, Denmark.
Dissing
Carsten
C
Søtofte
Inger
I
Norrby
Per-Ola
PO
Johannsen
Mogens
M
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
D005296:Ferrous Compounds; D000075163:Metallocenes; D015761:4-Aminopyridine; C003885:4-dimethylaminopyridine; C004998:ferrocene