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Nature of Proline-induced Enantiodifferentiation in Asymmetric Pd Catalyzed Hydrogenations: Is the Catalyst Really Indifferent?

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Abstract

The mode of enantioselection in the proline modified asymmetric hydrogenation of isophorone (3,5,5-trimethyl-2-cyclohexenone) on supported Pd catalysts has been studied. It is shown that several experimental factors, such as modifier structure and chemical nature of the catalyst support, strongly affect the outcome of the hydrogenations. Secondary kinetic resolution was found to be the major reason for obtaining high enantioselectivities on most catalysts. Extensive studies have been carried out to clarify the importance of the interaction of the proline–dihydroisophorone complex with the catalyst. The secondary kinetic resolution of dihydroisophorone was investigated under different conditions. First, racemic-dihydroisophorone was studied using several (S)-proline modified supported Pd catalysts, then the individual enantiomers were subjected to a similar reaction on Pd/BaCO3 catalyst in the presence of (S)-proline. Our results provide convincing support for the heterogeneous enantioselection model under the current experimental conditions.

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Acknowledgments

Financial support provided by the ACS-Petroleum Research Fund, University of Massachusetts Boston and Michigan Technological University is highly appreciated.

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Authors and Affiliations

  1. Department of Chemistry, University of Massachusetts Boston, 100 Morrissey Blvd, Boston, MA, 02125, USA

    Shilpa C. Mhadgut, Marianna Török, Sujaya Dasgupta & Béla Török

  2. Michigan Technological University, 1400 Townsend Drive, Houghton, MI, 49931, USA

    Shilpa C. Mhadgut, Marianna Török & Béla Török

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  1. Shilpa C. Mhadgut
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  2. Marianna Török
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  4. Béla Török
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Correspondence to Béla Török.

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Mhadgut, S.C., Török, M., Dasgupta, S. et al. Nature of Proline-induced Enantiodifferentiation in Asymmetric Pd Catalyzed Hydrogenations: Is the Catalyst Really Indifferent?. Catal Lett 123, 156–163 (2008). https://doi.org/10.1007/s10562-008-9411-y

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