Asymmetric catalytic hydrogenation. Design of new Ru catalysts and chiral ligands: from laboratory to industrial applications.
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)(eta(6)-cot)]BF(4). 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).
Genet
Jean-Pierre
JP
Ecole Nationale Supérieure de Chimie de Paris, Laboratoire de Synthèse Sélective Organique et Produits Naturels, 11 rue P. et M. Curie, 75231 Paris Cedex 05, France.
D000475:Alkenes / Q000737:chemistry; D002384:Catalysis; D003500:Cyclization; D015195:Drug Design; D006571:Heterocyclic Compounds / Q000138:chemical synthesis / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry; D006865:Hydrogenation; D007659:Ketones / Q000737:chemistry; D007700:Kinetics; D008024:Ligands; D008956:Models, Chemical; D008968:Molecular Conformation; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010720:Phosphines / Q000737:chemistry; D012238:Rhodium / Q000737:chemistry; D012428:Ruthenium / Q000737:chemistry*; D013237:Stereoisomerism
D000475:Alkenes; D006571:Heterocyclic Compounds; D007659:Ketones; D008024:Ligands; D009942:Organometallic Compounds; D010720:Phosphines; D012428:Ruthenium; D006859:Hydrogen; D012238:Rhodium