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 RuCl 2(η 1-Ph 2PCH 2CH 2OCH 3) 2(diamine) complexes 2L 1 – 2L 5 have been prepared in high yields from the reaction of equimolar amounts of RuCl 2(η 2-Ph 2PCH 2CH 2OCH 3) 2 1 with various kinds of chelating diamines L 1 – L 5 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.