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  • Review Article
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Bifunctional organic photocatalysts for enantioselective visible-light-mediated photocatalysis

Nature Synthesis volume 2, pages 913–925 (2023)Cite this article

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Abstract

This Review aims to highlight the developments in the field of visible-light-mediated enantioselective photocatalysis utilizing bifunctional organic photocatalysts by giving an overview of the existing hybrid structures and a summary of the reactions in which they have been employed. Organic bifunctional structures in this context are defined as the combination of organic photocatalyst moieties that can be activated by visible light with chiral catalysts responsible for enantioselective induction. An emphasis is put on comparing hybrid systems with dual-catalytic versions featuring two discrete catalysts, when applicable, while also pointing out limitations of current designs. Furthermore, mechanistic considerations are discussed, along with possible future directions in the development of new hybrid catalysts and the reactions that might benefit from these bifunctional structures.

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Fig. 1: Simplified overview of SET and EnT mechanisms in photocatalysis.
Fig. 2: Visible-light-mediated reactions catalysed by chiral bifunctional thioxanthone 1 and the structure of achiral thioxanthone 2.
Fig. 3: Enantioselective aerobic oxidation of β‑ketoesters utilizing bifunctional PCs.
Fig. 4: Bifunctional urea PCs.
Fig. 5: Chiral bifunctional photoaminocatalysts for the asymmetrical alkylation of aldehydes.
Fig. 6: Overview of visible-light-absorbing bifunctional CPA-PCs.
Fig. 7: Enantioselective reactions catalysed by chiral photo-phosphoric acid catalysts.
Fig. 8: Enantioselective reactions catalysed by chiral cyanoarene-based photo-phosphoric acid catalysts.

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Acknowledgements

A.B.R. thanks J. S. Tracy (University of West Florida) for helpful discussions and proofreading of the manuscript.

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  1. Institute of Organic Chemistry, Faculty of Chemistry and Pharmacy, University of Regensburg, Regensburg, Germany

    Alessa B. Rolka & Burkhard König

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A.B.R. wrote the manuscript. B.K. contributed to the discussion and helped revise the manuscript before submission.

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Rolka, A.B., König, B. Bifunctional organic photocatalysts for enantioselective visible-light-mediated photocatalysis. Nat. Synth 2, 913–925 (2023). https://doi.org/10.1038/s44160-023-00398-0

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