Asymmetric Catalytic Hydrogenation. Design of New Ru Catalysts and Chiral Ligands: From Laboratory to Industrial Applications
Top Cited Papers
- 14 November 2003
- journal article
- research article
- Published by American Chemical Society (ACS) in Accounts of Chemical Research
- Vol. 36 (12) , 908-918
- https://doi.org/10.1021/ar020152u
Abstract
This Account covers the design of Ru catalysts and ligands. Two classes of chiral phosphine ligands are prepared: the electron-rich trans-2,4-substituted phosphetanes, readily available from optically pure 1,3-diol cyclic sulfates, and atropoisomeric ligands (SYNPHOS, MeO-NAPhePHOS, bearing heterotopic biaryl moieties, and a chiral water-soluble diguanidinium binaphthyl diphosphine, Digm-BINAP). Applications of these ligands to rhodium- and ruthenium-mediated hydrogenation of ketones and olefins have been reported with high enantioselectivities. The recognition abilities of Ru-SYNPHOS for a wide range of ketones is superior to those observed with BINAP, MeO-NAPhePHOS, and MeO-BIPHEP. Several biologically active compounds have been prepared through dynamic kinetic resolution. This work gives access to a number of highly active catalysts of the type [Ru(biphosphane)(H)(η6-cot)]BF4. These catalysts have demonstrated their utility in the enantioselective hydrogenation of the tetrasubstituted cyclopentenone “dehydrodione”, which leads to the commercially important perfume component Paradisone (Firmenich).Keywords
This publication has 39 references indexed in Scilit:
- Asymmetric Catalysis: Science and Opportunities (Nobel Lecture) Copyright© The Nobel Foundation 2002. We thank the Nobel Foundation, Stockholm, for permission to print this lecture.Angewandte Chemie International Edition in English, 2002
- Mechanism of Asymmetric Hydrogenation of α-(Acylamino)acrylic Esters Catalyzed by BINAP−Ruthenium(II) DiacetateJournal of the American Chemical Society, 2002
- Large-Scale Candoxatril Asymmetric HydrogenationOrganic Process Research & Development, 2001
- Industrial Synthesis of (+)-cis-Methyl Dihydrojasmonate by Enantioselective Catalytic Hydrogenation; Identification of the Precatalyst [Ru((−)-Me-DuPHOS)(H)(η6-1,3,5-cyclooctatriene)](BF4)Angewandte Chemie International Edition in English, 2000
- Asymmetric Synthesis of Biaryls by Intramolecular Oxidative Couplings of Cyanocuprate IntermediatesAngewandte Chemie International Edition in English, 1994
- Ruthenium-catalyzed oxidation of amides and lactams with peroxidesJournal of the American Chemical Society, 1990
- Asymmetric synthesis of isoquinoline alkaloids by homogeneous catalysisJournal of the American Chemical Society, 1986
- Asymmetric catalytic reduction with transition metal complexes. I. Catalytic system of rhodium(I) with (-)-2,3-0-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane, a new chiral diphosphineJournal of the American Chemical Society, 1972
- The asymmetric synthesis of hydratropic acid and amino-acids by homogeneous catalytic hydrogenationJournal of the Chemical Society D: Chemical Communications, 1971
- Asymmetric Catalytic Hydrogenation with an Optically Active Phosphinerhodium Complex in Homogeneous SolutionAngewandte Chemie International Edition in English, 1968