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Asymmetric hydrogenation of an ,-unsaturated ketone by diamine(ether-phosphine)ruthenium(II) complexes and lipase-catalyzed kinetic resolution: a consecutive approach

Citation

Lindner, E and Ghanem, A and Warad, I and Eichele, K and Mayer, H and Schurig, V, Asymmetric hydrogenation of an a,a-unsaturated ketone by diamine(ether-phosphine)ruthenium(II) complexes and lipase-catalyzed kinetic resolution: a consecutive approach, Tetrahedron: Asymmetry, 14, (8) pp. 1045-1053. ISSN 0957-4166 (2003) [Refereed Article]


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DOI: doi:10.1016/S0957-4166(03)00129-0

Abstract

The RuCl2(1-Ph2PCH2CH2OCH3)2(diamine) complexes 2L12L5 have been prepared in high yields from the reaction of equimolar amounts of RuCl2(2-Ph2PCH2CH2OCH3)2 1 with various kinds of chelating diamines L1L5 to form five-membered chelates with ruthenium. These novel ruthenium(II) complexes have been used as catalysts in the asymmetric hydrogenation of the prochiral ketone trans-4-phenyl-3-butene-2-one 3, using 2-propanol and different types of cocatalysts. Whereas complexes with achiral diamines afforded the racemic alcohols, complexes with chiral diamines (R,R or S,S) allowed the formation of the corresponding enantiomerically enriched secondary alcohol (S or R) with ee values of 45%. In order to obtain the secondary alcohol with ee of >99%, the kinetic resolution of enantiomerically enriched trans-4-phenyl-3-butene-2-ol 3 was performed in a consecutive approach using either the lipase-catalyzed enantioselective transesterification of the alcohol with isopropenyl acetate as the acyl donor in toluene or the enantioselective hydrolysis of the corresponding acetate in buffer. The determination of the enantiomeric excess (ee) of the resulting enantiomerically enriched secondary alcohols was performed by gas chromatography using heptakis(2,3-di-O-methyl-6-O-tert-butyldimethylsilyl)--cyclodextrin as the chiral stationary phase.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Organic Chemistry
Research Field:Organic Green Chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding Knowledge
Objective Field:Expanding Knowledge in the Chemical Sciences
Author:Ghanem, A (Dr Ashraf Ghanem)
ID Code:57749
Year Published:2003
Web of Science® Times Cited:40
Deposited By:Austn Centre for Research in Separation Science
Deposited On:2009-08-12
Last Modified:2009-08-13
Downloads:0

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