Transfer Hydrogenation of Activated CC Bonds Catalyzed by Ruthenium Amido Complexes: Reaction Scope, Limitation, and Enantioselectivity
- 1 April 2005
- journal article
- research article
- Published by American Chemical Society (ACS) in The Journal of Organic Chemistry
- Vol. 70 (9) , 3584-3591
- https://doi.org/10.1021/jo0478205
Abstract
It was found that the chemoselectivity could be completely switched from CO to CC bonds in the transfer hydrogenation of activated α,β-unsaturated ketones catalyzed by diamine−ruthenium complex. Moreover, this addition via metal hydride had been applied to the reduction of various activated olefins. The electron-withdrawing ability of functional groups substituted on CC bonds at the α- or β-position had strong influence on the reactivity. In addition, a wide variety of chiral diamine−Ru(II)−(arene) systems was investigated to explore the asymmetric transfer hydrogenation of prochiral α,α-dicyanoolefins. Two parameters had been systematically studied, (i) the structure of the N-sulfonylated chiral diamine ligands, in which several chiral diamines substituted on the benzene ring of DPEN were first reported, and (ii) the structure of the metal precursors, and high enantioselectivitiy (up to 89% ee) at the β-carbon was obtained.Keywords
This publication has 37 references indexed in Scilit:
- Mechanistic Aspects of Formation of Chiral Ruthenium Hydride Complexes from 16‐Electron Ruthenium Amide Complexes and Formic Acid: Facile Reversible Decarboxylation and CarboxylationAdvanced Synthesis & Catalysis, 2004
- Dendritic catalysts for asymmetric transfer hydrogenationChemical Communications, 2001
- The Catalyst Precursor, Catalyst, and Intermediate in the RuII‐Promoted Asymmetric Hydrogen Transfer between Alcohols and KetonesAngewandte Chemie International Edition in English, 1997
- Kinetic Resolution of Racemic Secondary Alcohols by RuII‐Catalyzed Hydrogen TransferAngewandte Chemie International Edition in English, 1997
- Asymmetric Transfer Hydrogenation Catalyzed by Chiral Ruthenium ComplexesAccounts of Chemical Research, 1997
- Asymmetric catalysis. 80. Mechanistic aspects of the rhodium-catalyzed enantioselective transfer hydrogenation of .alpha.,.beta.-unsaturated carboxylic acids using formic acid/triethylamine (5:2) as the hydrogen sourceJournal of the American Chemical Society, 1993
- Enantioselective Catalysis, Part 481: Highly Enantioselective Catalytic Transfer-Hydrogenation of Itaconic Acid with FormatesSynthesis, 1989
- Enantioselective Catalytic Transfer‐Hydrogenation of α,β‐Unsaturated Carboxylic Acids with Triethylammonium FormateAngewandte Chemie International Edition in English, 1988
- Heterogeneous catalytic transfer hydrogenation and its relation to other methods for reduction of organic compoundsChemical Reviews, 1985
- Arene ruthenium(II) complexes formed by dehydrogenation of cyclohexadienes with ruthenium(III) trichlorideJ. Chem. Soc., Dalton Trans., 1974