Asymmetric hydrogenation of prochiral ketones by amberlite-supported rhodium(I) chiral diphosphine complexes

1981 ◽  
Vol 17 (7-8) ◽  
pp. 215-218 ◽  
Author(s):  
K. Ohkubo ◽  
M. Haga ◽  
K. Yoshinaga ◽  
Y. Motozato
Author(s):  
Ryoji Noyori ◽  
Christian A Sandoval ◽  
Kilian Muñiz ◽  
Takeshi Ohkuma

Chiral diphosphine/1,2-diamine–Ru(II) complexes catalyse the rapid, productive and enantioselective hydrogenation of simple ketones. The carbonyl-selective hydrogenation takes place via a non-classical metal–ligand bifunctional mechanism. The reduction of the C=O function occurs in the outer coordination sphere of an 18e trans -RuH 2 (diphosphine)(diamine) complex without interaction between the unsaturated moiety and the metallic centre. The Ru atom donates a hydride and the NH 2 ligand delivers a proton through a pericyclic six-membered transition state, directly giving an alcoholic product without metal alkoxide formation. The enantiofaces of prochiral ketones are differentiated on the chiral molecular surface of the saturated RuH 2 species. This asymmetric catalysis manifests the significance of ‘kinetic’ supramolecular chemistry.


2010 ◽  
Vol 31 (3) ◽  
pp. 273-277
Author(s):  
Jinbo WANG ◽  
Ruixiang QIN ◽  
Wei XIONG ◽  
Yun JIA ◽  
Derong LIU ◽  
...  

Author(s):  
Robert B. Jordan

This third edition retains the general level and scope of earlier editions, but has been substantially updated with over 900 new references covering the literature through 2005, and 140 more pages of text than the previous edition. In addition to the general updating of materials, there is new or greatly expanded coverage of topics such as Curtin-Hammett conditions, pressure effects, metal hydrides and asymmetric hydrogenation catalysts, the inverted electron-transfer region, intervalence electron transfer, photochemistry of metal carbonyls, methyl transferase and nitric oxide synthase. The new chapter on heterogeneous systems introduces the basic background to this industrially important area. The emphasis is on inorganic examples of gas/liquid and gas/liquid/solid systems and methods of determining heterogeneity.


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