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Catalytic enantioselective syn hydration of enones in water using a DNA-based catalyst

Nature Chemistry volume 2, pages 991–995 (2010)Cite this article

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Abstract

The enantioselective addition of water to olefins in an aqueous environment is a common transformation in biological systems, but was beyond the ability of synthetic chemists. Here, we present the first examples of a non-enzymatic catalytic enantioselective hydration of enones, for which we used a catalyst that comprises a copper complex, based on an achiral ligand, non-covalently bound to (deoxy)ribonucleic acid, which is the only source of chirality present under the reaction conditions. The chiral β-hydroxy ketone product was obtained in up to 82% enantiomeric excess. Deuterium-labelling studies demonstrated that the reaction is diastereospecific, with only the syn hydration product formed. So far, this diastereospecific and enantioselective reaction had no equivalent in conventional homogeneous catalysis.

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Figure 1: Enantioselective hydration of α,β-unsaturated ketones.
Figure 2: Temporal evolution of enantiomeric excess and conversion.
Figure 3: Diastereospecificity of the catalytic hydration reaction.

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Acknowledgements

This work was supported by grants from the National Research School Combination – Catalysis, the European Research Area Chemistry program and the Netherlands Organisation for Scientific Research.

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Authors and Affiliations

  1. Stratingh Institute for Chemistry and Center for Systems Chemistry, University of Groningen, Nijenborgh 4, Groningen, 9747, AG, The Netherlands

    Arnold J. Boersma, David Coquière, Danny Geerdink, Fiora Rosati, Ben L. Feringa & Gerard Roelfes

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  1. Arnold J. Boersma
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  2. David Coquière
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  3. Danny Geerdink
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  4. Fiora Rosati
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  5. Ben L. Feringa
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Contributions

A.J.B., B.L.F. and G.R. conceived the project; A.J.B., D.C. and G.R. designed the experiments; A.J.B., D.C., D.G. and F.R. performed the experiments and analysed the data. A.J.B., B.L.F. and G.R. co-wrote the paper. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Ben L. Feringa or Gerard Roelfes.

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The authors declare no competing financial interests.

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Boersma, A., Coquière, D., Geerdink, D. et al. Catalytic enantioselective syn hydration of enones in water using a DNA-based catalyst. Nature Chem 2, 991–995 (2010). https://doi.org/10.1038/nchem.819

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