https://pubs.rsc.org/en/content/articlepdf/2019/NP/C8NP00092A

Marine natural products.

2.5. Stabilization of IL Emulsions by Nanoparticles 2623 3. Hydrogenations in ILs 2623 3.1. Hydrogenation on IL-Stabilized Nanoparticles 2623 3.1.1. Hydrogenation of 1,3-Butadiene 2623 3.1.2. Hydrogenation of Alkenes and Arenes 2624 3.1.3. Hydrogenation of Ketones 2624 3.2. Homogeneous Catalytic Hydrogenation in ILs 2624 3.3. Hydrogenation of Functionalized ILs 2625 3.3.1. Selective Hydrogenation of Polymers 2625 3.4. Asymmetric Hydrogenations 2626 3.4.1. Enantioselective Hydrogenation 2626 3.5. Role of the ILs Purity in Hydrogenation Reactions 2628

Catalysis in ionic liquids

The increasing demand to produce enantiomerically pure pharmaceuticals, agrochemicals, flavors, and other fine chemicals has advanced the field of asymmetric catalytic technologies.1,2 Among all asymmetric catalytic methods, asymmetric hydrogenation utilizing molecular hydrogen to reduce prochiral olefins, ketones, and imines, have become one of the most efficient methods for constructing chiral compounds.3 The development of homogeneous asymmetric hydrogenation was initiated by Knowles4a and Horner4b in the late 1960s, after the discovery of Wilkinson’s homogeneous hydrogenation catalyst [RhCl(PPh3)3]. By replacing triphenylphosphine of the Wilkinson’s catalystwithresolvedchiralmonophosphines,6Knowles and Horner reported the earliest examples of enantioselective hydrogenation, albeit with poor enantioselectivity. Further exploration by Knowles with an improved monophosphine CAMP provided 88% ee in hydrogenation of dehydroamino acids.7 Later, two breakthroughs were made in asymmetric hydrogenation by Kagan and Knowles, respectively. Kagan reported the first bisphosphine ligand, DIOP, for Rhcatalyzed asymmetric hydrogenation.8 The successful application of DIOP resulted in several significant directions for ligand design in asymmetric hydrogenation. Chelating bisphosphorus ligands could lead to superior enantioselectivity compared to monodentate phosphines. Additionally, P-chiral phosphorus ligands were not necessary for achieving high enantioselectivity, and ligands with backbone chirality could also provide excellent ee’s in asymmetric hydrogenation. Furthermore, C2 symmetry was an important structural feature for developing new efficient chiral ligands. Kagan’s seminal work immediately led to the rapid development of chiral bisphosphorus ligands. Knowles made his significant discovery of a C2-symmetric chelating bisphosphine ligand, DIPAMP.9 Due to its high catalytic efficiency in Rh-catalyzed asymmetric hydrogenation of dehydroamino acids, DIPAMP was quickly employed in the industrial production of L-DOPA.10 The success of practical synthesis of L-DOPA via asymmetric hydrogenation constituted a milestone work and for this work Knowles was awarded the Nobel Prize in 2001.3k This work has enlightened chemists to realize * Corresponding author. 3029 Chem. Rev. 2003, 103, 3029−3069

New Chiral Phosphorus Ligands for Enantioselective Hydrogenation

Practical methodologies for the synthesis of indoles.

Asymmetric 1,3-Dipolar Cycloaddition Reactions

Hydrogenation asymetrique en alcool de diverses cetones (aminocetones, cetols, cetoesters, cetoamides, cetothioester, cetoethers, dicetones, cetoacide) catalysee par des complexes du ruthenium(II) et du bis-diphenylphosphino-2,2' binaphtyle-1,1'

Homogeneous asymmetric hydrogenation of functionalized ketones

Hydrogenation d'acides, d'hydroxyacides, et de diacides vinyliques. Application a la synthese du naproxene a partir de l'acide [methoxy-6 naphtyl-2]-2 acrylique

Asymmetric hydrogenation of unsaturated carboxylic acids catalyzed by BINAP-ruthenium(II) complexes

Asymmetric synthesis of isoquinoline alkaloids by homogeneous catalysis

Hydrogenation enantioselective en particulier du geraniol et du nerol catalysee par des complexes dicarboxylato du ruthenium(II) contenant des coordinats bis-diarylphosphino-2,2' binaphtyles-1,1'

Enantioselective hydrogenation of allylic and homoallylic alcohols

Des aminoarenes sont transformes directement en amines secondaires et tertiaires par reaction a 150-180°C avec des alcools primaires en presence de catalyseurs complexes de Ru dont le plus actif est le dichloro-tris(triphenylphosphine)-Ru. Cinetique. On propose un cycle catalytique qui met en jeu une attaque nucleophile de l'aminoarene sur un aldehyde intermediaire

Tetsuo Ohta

Papers

Homogeneous asymmetric hydrogenation of functionalized ketones

Asymmetric hydrogenation of unsaturated carboxylic acids catalyzed by BINAP-ruthenium(II) complexes

Asymmetric synthesis of isoquinoline alkaloids by homogeneous catalysis

Enantioselective hydrogenation of allylic and homoallylic alcohols

Ruthenium-catalyzed N-alkylation and N-benzylation of aminoarenes with alcohols