Asymmetric catalytic hydrogenation. Design of new Ru catalysts and chiral ligands: From laboratory to industrial applications

被引:220
作者
Genet, JP [1 ]
机构
[1] Ecole Natl Super Chim Paris, Lab Synth Select Organ & Prod, F-75231 Paris 05, France
关键词
D O I
10.1021/ar020152u
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
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)]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).
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收藏
页码:908 / 918
页数:11
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