ENANTIOSELECTIVE HYDROGENATION OF ALPHA-KETOESTERS OVER PT/ALUMINA MODIFIED WITH CINCHONIDINE - THEORETICAL INVESTIGATION OF THE SUBSTRATE-MODIFIER INTERACTION

Enantio-differentiation in the asymmetric hydrogenation of alpha-ketoesters to alpha-hydroxyesters over platinum catalysts modified with cinchona-alkaloid modifiers occurs through interaction of the ketoester with the cinchona modifier. The structure of the probable transition complex has been calculated for the system methyl pyruvate (substrate)-cinchonidine (modifier) using molecular mechanics and quantum chemistry techniques at both ab initio and semi-empirical levels. The calculations suggest that protonated cinchonidine is energetically more likely to interact with the substrate and that the crucial interaction occurs via hydrogen bonding of the quinuclidine nitrogen and the oxygen of the alpha-carbonyl moiety of methyl pyruvate. In this complex the methyl pyruvate is transformed into a half-hydrogenated species which is adsorbed on the platinum surface and on hydrogenation yields the product methyl lactate. Theoretical studies indicate that adsorption of the complex leading to (R)-methyl lactate is energetically more favourable than that of the corresponding complex which yields (S)-methyl lactate, which may be the key for the enantio-differentiation.