Homogeneous hydrogenation of ketones in the presence of H2Ru(CO)(2)(PPh3)(2)

The hydrogenation of ketones to alcohols in the presence of a hydride ruthe nium triphenylphosphine complex, H2Ru(CO)(2)(Ph-3)(2), has been investigate d. Acetophenone was hydrogenated at 120 degrees C with a conversion of 69% after 24 h, The yield is 85% working at 140 degrees C, A kinetic investigat ion of the reaction was also performed: the reaction is first order with re spect to the hydrogen pressure, substrate and catalyst concentration. The r ate of hydrogenation depends on the nature of the substrate: steric and ele ctronic effects have a strong influence on the hydrogenation of ketones, 2, 2-Trifluoroacetophenone is almost completely hydrogenated at 120 degrees C after 3 h, A mechanism has been tentatively suggested for the hydrogenation of ketones in which the coordination of the substrate to the metal is foll owed by its insertion into the ruthenium-hydrido bond with formation of the corresponding alkoxide, This complex reacts' with hydrogen, restoring the catalyst and forming the alcohol, We have also tested the activity of this catalyst in the hydrogenation of an alpha;beta-unsaturated ketone (trans-4- phenylbut-3-en-2-one), The C=C double bond is preferentially hydrogenated w ith a high chemoselectivity (92.4% at 100 degrees C). The data collected on the hydrogenation of trans-4-phenylbut-3-en-2-one suggest a different mech anism in which the rate-determining step is the interaction between the C=C double bond of the ketone,vith the metal-hydrido bond. Experimental eviden ce is re-ported to support this different hypothesis, Copyright (C) 2000 Jo hn Wiley & Sons, Ltd.