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Enantio-differentiating hydrogenation of methyl acetoacetate over tartaric acid modified Ni catalyst at atmospheric pressure of hydrogen assisted by hydrogen transfer reaction

Tsutomu Osawa, Satoru Kawajiri, Anna Ishisaki

Reaction Kinetics, Mechanisms and Catalysis(2016)

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Abstract
The enantio-differentiating hydrogenation of methyl acetoacetate was carried out under the atmospheric pressure of hydrogen (gauge pressure: 0 MPa) assisted by hydrogen transfer from 2-propanol. It was revealed that the tartaric acid-NaBr-modified supported nickel catalyst, especially Ni/CeO 2 , produced a higher enantioselectivity than the modified Raney nickel catalyst under the atmospheric pressure of hydrogen. Catalyst preparation and hydrogenation conditions for the hydrogenation over the modified Ni/CeO 2 were studied. The Ni/CeO 2 prepared by calcination at 773 K and reduction at 773 K gave the best result. The enantioselectivity of 64 % (22 % conversion) was attained under the atmospheric pressure of hydrogen at 323 K assisted the by hydrogen transfer from the solvent.
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Key words
Enantio-differentiating hydrogenation,Hydrogen transfer,Tartaric acid modified Ni/CeO2,Methyl acetoacetate
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