Chiral Induction Effects in Ruthenium(II) Amino Alcohol Catalysed Asymmetric Transfer Hydrogenation of Ketones: An Experimental and Theoretical Approach

• Published in: Chemistry : a European journal Vol. 6; no. 15; pp. 2818 - 2829
• Main Authors: Petra, Daniëlle G. I., Reek, Joost N. H., Handgraaf, Jan-Willem, Meijer, Evert Jan, Dierkes, Peter, Kamer, Paul C. J., Brussee, Johannes, Schoemaker, Hans E., van Leeuwen, Piet W. N. M.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 04.08.2000; WILEY‐VCH Verlag
• Subjects: asymmetric catalysis; density functional calculations; hydrogen transfer; reaction mechanisms; ruthenium
• ISSN: 0947-6539; 1521-3765
• DOI: 10.1002/1521-3765(20000804)6:15<2818::AID-CHEM2818>3.0.CO;2-Q

The enantioselective outcome of transfer hydrogenation reactions that are catalysed by ruthenium(II) amino alcohol complexes was studied by means of a systematically varied series of ligands. It was found that both the substituent at the 1‐position in the 2‐amino‐1‐alcohol ligand and the substituent at the amine functionality influence the enantioselectivity of the reaction to a large extent: enantioselectivities (ee values) of up to 95 % were obtained for the reduction of acetophenone. The catalytic cycle of ruthenium(II) amino alcohol catalysed transfer hydrogenation was examined at the density functional theory level. The formation of a hydrogen bond between the carbonyl functionality of the substrate and the amine proton of the ligand, as well as the formation of an intramolecular H⋅⋅⋅H bond and a planar H‐Ru‐NH moiety are crucially important for the reaction mechanism. The enantioselective outcome of the reaction can be illustrated with the aid of molecular modelling by the visualisation of the steric interactions between the ketone and the ligand backbone in the ruthenium(II) catalysts.