title: Enantioselective synthesis of DIANANE, a novel C2-symmetric chiral diamine for asymmetric catalysis.
abstract: DIANANE (endo,endo-2,5-diaminonorbornane) is a novel chiral C(2)-symmetric diamine, based on the rigid bicyclo[2.2.1]heptane scaffold. Schiff-base ligands derived from DIANANE have already found use in asymmetric catalysis, e.g., in the highly enantioselective Nozaki-Hiyama-Kishi reaction. We herein describe a practical synthesis of enantiomerically pure DIANANE, starting from norbornadiene in four steps: (i) Pd-MOP catalyzed Hayashi-hydrosilylation/Tamao-Fleming oxidation, (ii) oxidation to norbornane-2,5-dione, (iii) endo-selective reductive amination with benzylamine, and (iv) hydrogenolytic debenzylation. None of the steps involves chromatographic purification. For the Tamao-Fleming oxidation, the use of hydrogen peroxide in the form of its urea clathrate instead of aqueous solution proved beneficial. By the above sequence, enantiomerically pure (ee >or=99%) DIANANE was obtained from norbornadiene in 40-50% overall yield. The relative and absolute configuration of DIANANE was confirmed by X-ray crystallography of the DIANANE bis-tosylamide, and of its bis-camphorsulfonamide. Furthermore, the synthesis and X-ray crystal structure of the Schiff-base ligand derived from DIANANE and 3,5-di-tert-butyl salicylic aldehyde are reported.
authors.affiliation: Institut für Organische Chemie, Universität zu Köln, Greinstrasse 4, D-50939 Köln, Germany. berkessel@uni-koeln.de
authors.forename: Albrecht
authors.initials: A
authors.lastname: Berkessel
authors.forename: Michael
authors.initials: M
authors.lastname: Schröder
authors.forename: Christoph A
authors.initials: CA
authors.lastname: Sklorz
authors.forename: Stefania
authors.initials: S
authors.lastname: Tabanella
authors.forename: Nadine
authors.initials: N
authors.lastname: Vogl
authors.forename: Johann
authors.initials: J
authors.lastname: Lex
authors.forename: Jörg M
authors.initials: JM
authors.lastname: Neudörfl