Metal—Ligand Bifunctional Catalysis for Asymmetric Hydrogenation

ChemInform ◽  
2006 ◽  
Vol 37 (24) ◽  
Author(s):  
Ryoji Noyori ◽  
Christian A. Sandoval ◽  
Kilian Muniz ◽  
Takeshi Ohkuma
ChemInform ◽  
2008 ◽  
Vol 39 (3) ◽  
Author(s):  
Ryoji Noyori ◽  
Takeshi Ohkuma ◽  
Christian A. Sandoval ◽  
Kilian Muniz

ChemInform ◽  
2010 ◽  
Vol 41 (38) ◽  
pp. no-no
Author(s):  
Ryoji Noyori ◽  
Takeshi Ohkuma ◽  
Christian A. Sandoval ◽  
Kilian Muniz

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.


2001 ◽  
Vol 73 (2) ◽  
pp. 227-232 ◽  
Author(s):  
Ryoji Noyori ◽  
Masatoshi Koizumi ◽  
Dai Ishii ◽  
Takeshi Ohkuma

RuCl2 (phosphine) 2 (1,2-diamine) complexes, coupled with an alkaline base in 2-propanol, allows for preferential hydrogenation of a C=O function over coexisting conjugated or nonconjugated C=C linkages, a nitro group, halogen atoms, and various heterocycles. The functional group selectivity is based on the novel metal-ligand bifunctional mechanism. The use of appropriate chiral diphosphines and diamines results in rapid and productive asymmetric hydrogenation of a range of aromatic, hetero-aromatic, and olefinic ketones. The versatility of this method is manifested by the asymmetric synthesis of various biologically significant chiral compounds.


2021 ◽  
Author(s):  
Kuo-Wei Huang ◽  
Theo P Goncalves ◽  
Indranil Dutta

Unlike the conventional model of transition metal catalysis, ligands in metal–ligand cooperative (or bifunctional) catalysis are involved in the substrate activations. Such processes have offered unique mechanistic understandings and led...


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