Stereochemical Investigation on Asymmetrically Modified Raney Nickel Catalyst. Mode of Interaction between Modifying Reagent and Substrate in the Enantioface-differentiating Process

The mode of enantioface-differentiating hydrogenation with asymmetrically modified Raney nickel (MRNi) was investigated by using various sorts of modifying reagents and substrates. The optical yields (O.Y.) of the hydrogenation of methyl acetoacetate over MRNi for different modifying reagents occured in the following order: (Remark: Graphics omitted.), (Remark: Graphics omitted.). The hydrogenation of various substrates of the structure, (Remark: Graphics omitted.), over tartaric acid-modified Raney nickel (TA–MRNi), gave high optical yields only when the substituent –Y functioned as a good hydrogen bond acceptor like a carbonyl group, and two pairs of hydrogen bondings between substrate and two hydroxyl groups of tartaric acid were available. As for the stereochemistry of the reaction in such a case, (R,R)-TA–MRNi always gave (R)-product in excess. Based on the stereochemistry of the reaction and the role of hydrogen bonds between modifying reagent and substrate, a stereochemical model is proposed to elucidate the mode of enantioface-differentiating hydrogenation of prochiral ketones over TA–MRNi.