Enhancing the potential of enantioselective organocatalysis with light

Abstract

Organocatalysis—catalysis mediated by small chiral organic molecules—is a powerful technology for enantioselective synthesis, and has extensive applications in traditional ionic, two-electron-pair reactivity domains. Recently, organocatalysis has been successfully combined with photochemical reactivity to unlock previously inaccessible reaction pathways, thereby creating new synthetic opportunities. Here we describe the historical context, scientific reasoning and landmark discoveries that were essential in expanding the functions of organocatalysis to include one-electron-mediated chemistry and excited-state reactivity.

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Figure 1: Merging photoredox and enamine catalysis.
Figure 2: Merging photoredox and covalent organocatalysis.
Figure 3: Merging photoredox and non-covalent organocatalysis.
Figure 4: Excited-state reactivity of chiral organocatalytic intermediates.
Figure 5: Non-covalent interactions in enantioselective photochemistry.

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Acknowledgements

P.M. thanks the Generalitat de Catalunya (CERCA Program), Agencia Estatal de Investigación (AEI) (CTQ2016-75520-P), and the European Research Council (ERC 681840-CATA-LUX) for financial support. M.S. thanks the EU for a Horizon 2020 Marie Skłodowska-Curie Fellowship (grant 744242).

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P.M. outlined the content of the Review and defined its scope. M.S. and P.M. worked together to prepare and edit the manuscript, figures and references.

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Correspondence to Paolo Melchiorre.

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Silvi, M., Melchiorre, P. Enhancing the potential of enantioselective organocatalysis with light. Nature 554, 41–49 (2018). https://doi.org/10.1038/nature25175

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