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J Am Chem Soc. 2005 Nov 2;127(43):15083-90.

Mechanistic insights into the phosphine-free RuCp*-diamine-catalyzed hydrogenation of aryl ketones: experimental and theoretical evidence for an alcohol-mediated dihydrogen activation.

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1
Organic Chemistry, Department of Chemistry, Uppsala University, Uppsala, Sweden.

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.

PMID:
16248647
DOI:
10.1021/ja051920q
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