Asymmetric hydrogenation of an α,β-unsaturated ketone by diamine(ether-phosphine)ruthenium(II) complexes and lipase-catalyzed kinetic resolution

A consecutive approach

Ekkehard Lindner, Ashraf Ghanem, Ismail Warad, Klaus Eichele, Hermann A. Mayer, Volker Schurig

Research output: Contribution to journalArticle

42 Citations (Scopus)

Abstract

The RuCl21-Ph2PCH2CH 2OCH3)2(diamine) complexes 2L1-2L5 have been prepared in high yields from the reaction of equimolar amounts of RuCl22-Ph2PCH2CH 2OCH3)2 1 with various kinds of chelating diamines L1-L5 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)-β-cyclodextrin as the chiral stationary phase.

Original languageEnglish
Pages (from-to)1045-1053
Number of pages9
JournalTetrahedron Asymmetry
Volume14
Issue number8
DOIs
Publication statusPublished - 18 Apr 2003
Externally publishedYes

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phosphine
Enzyme kinetics
Diamines
Ruthenium
Lipases
diamines
Ketones
Lipase
phosphines
ketones
Ether
ruthenium
Hydrogenation
hydrogenation
Ethers
ethers
alcohols
Alcohols
Kinetics
kinetics

Cite this

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title = "Asymmetric hydrogenation of an α,β-unsaturated ketone by diamine(ether-phosphine)ruthenium(II) complexes and lipase-catalyzed kinetic resolution: A consecutive approach",
abstract = "The RuCl2(η1-Ph2PCH2CH 2OCH3)2(diamine) complexes 2L1-2L5 have been prepared in high yields from the reaction of equimolar amounts of RuCl2(η2-Ph2PCH2CH 2OCH3)2 1 with various kinds of chelating diamines L1-L5 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)-β-cyclodextrin as the chiral stationary phase.",
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Asymmetric hydrogenation of an α,β-unsaturated ketone by diamine(ether-phosphine)ruthenium(II) complexes and lipase-catalyzed kinetic resolution : A consecutive approach. / Lindner, Ekkehard; Ghanem, Ashraf; Warad, Ismail; Eichele, Klaus; Mayer, Hermann A.; Schurig, Volker.

In: Tetrahedron Asymmetry, Vol. 14, No. 8, 18.04.2003, p. 1045-1053.

Research output: Contribution to journalArticle

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T1 - Asymmetric hydrogenation of an α,β-unsaturated ketone by diamine(ether-phosphine)ruthenium(II) complexes and lipase-catalyzed kinetic resolution

T2 - A consecutive approach

AU - Lindner, Ekkehard

AU - Ghanem, Ashraf

AU - Warad, Ismail

AU - Eichele, Klaus

AU - Mayer, Hermann A.

AU - Schurig, Volker

PY - 2003/4/18

Y1 - 2003/4/18

N2 - The RuCl2(η1-Ph2PCH2CH 2OCH3)2(diamine) complexes 2L1-2L5 have been prepared in high yields from the reaction of equimolar amounts of RuCl2(η2-Ph2PCH2CH 2OCH3)2 1 with various kinds of chelating diamines L1-L5 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)-β-cyclodextrin as the chiral stationary phase.

AB - The RuCl2(η1-Ph2PCH2CH 2OCH3)2(diamine) complexes 2L1-2L5 have been prepared in high yields from the reaction of equimolar amounts of RuCl2(η2-Ph2PCH2CH 2OCH3)2 1 with various kinds of chelating diamines L1-L5 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)-β-cyclodextrin as the chiral stationary phase.

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