Affiliation:
1. Department of Chemistry and Research Center for Materials Science, Nagoya University, Chikusa, Nagoya 464-8602, Japan
Abstract
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
-RuH
2
(diphosphine)(diamine) complex without interaction between the unsaturated moiety and the metallic centre. The Ru atom donates a hydride and the NH
2
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 RuH
2
species. This asymmetric catalysis manifests the significance of ‘kinetic’ supramolecular chemistry.
Subject
General Physics and Astronomy,General Engineering,General Mathematics
Cited by
102 articles.
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