title: Mechanistic insights into the phosphine-free RuCp*-diamine-catalyzed hydrogenation of aryl ketones: experimental and theoretical evidence for an alcohol-mediated dihydrogen activation.
abstract: The commercially available chiral diamine quincorine-amine, originally derived from quinine, was found to be a highly active catalyst for ruthenium-catalyzed hydrogenation of ketones. The complex formed between the quincorine-amine, containing both a primary and a quinuclidine amino function, and RuCp*Cl catalyzes the hydrogenation of aromatic and aliphatic ketones in up to 90% ee approximately 24 times faster than previously reported Ru-diamine complexes. The pseudo-enantiomer of the quincorine-amine, i.e., quincoridine-amine, also showed high activity; however, the enantioselectivities obtained with this catalyst were lower. The reason for the lower, but opposite stereoselectivity seen with the quincoridine-amine, as compared to the quincorine-amine, was rationalized by a kinetic and computational study of the mechanism of the reaction. The theoretical calculations also revealed a significantly lower activation barrier for the alcohol-mediated split of dihydrogen, as compared to the nonalcohol-mediated process, a finding of utmost implication also for the diphosphine/diamine-mediated enantioselective hydrogenation of ketones.
authors.affiliation: Organic Chemistry, Department of Chemistry, Uppsala University, Uppsala, Sweden.
authors.forename: Christian
authors.initials: C
authors.lastname: Hedberg
authors.forename: Klas
authors.initials: K
authors.lastname: Källström
authors.forename: Per I
authors.initials: PI
authors.lastname: Arvidsson
authors.forename: Peter
authors.initials: P
authors.lastname: Brandt
authors.forename: Pher G
authors.initials: PG
authors.lastname: Andersson