Chiral diphosphine/1,2-diamine-Ru(II) complexes catalyse the rapid, productive and enantioselective hydrogenation of simple ketones. The carbonyl-selective hydrogenation takes place via a non-classical metal-ligand bifunctional mechanism. The reduction of the C=O function occurs in the outer coordination sphere of an 18e trans-RuH2(diphosphine)(diamine) complex without interaction between the unsaturated moiety and the metallic centre. The Ru atom donates a hydride and the NH2 ligand delivers a proton through a pericyclic six-membered transition state, directly giving an alcoholic product without metal alkoxide formation. The enantiofaces of prochiral ketones are differentiated on the chiral molecular surface of the saturated RuH2 species. This asymmetric catalysis manifests the significance of 'kinetic' supramolecular chemistry.
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