Abstract
Enantioselective hydrogenation of seven different esters of phenylglyoxylic acid was investigated by variation of the bulkiness at ester side of the substrates [Ph C(O) C(O)OR, R = Me ( l), cyclohexyl ( 2), adamantyl ( 3), cis-decahydro-1-naphthyl ( 4), phenyl ( 5), 1-naphthyl ( 6), 2-naphthyl ( 7)] on Pt-alumina-cinchonidine (CD) and Pt-alumina- β-isocinchonine ( β-ICN) chiral catalysts using mild experimental conditions (273 K and room temperature, hydrogen pressure of 1–25 bar) in solvents of AcOH and toluene. Hydrogenation on Pt-alumina-CD chiral catalyst produced high values of ee for all but the 5 and 7 compounds. The formation of ( R)-mandelic acid esters was 86–91% in AcOH and 79–94% in toluene. The experiments verified the general applicability of the Orito reaction in the preparation of enantiomers of α-hydroxyesters. Under the experimental conditions applied, the magnitude of ee is affected by the steric size of α-ketoesters and by solvents. In the enantioselective hydrogenation of substrates over a Pt-alumina- β-ICN catalyst in toluene, inversion of enantioselectivity occurred; ( R)-mandelic acid esters formed with a medium ee of 30–54%. The conformation of the adsorbed modifier plays a more determining role than the bulkiness of the substrate in the formation of the intermediate complex responsible for enantioselection.
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