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Energy- and atom-efficient chemical synthesis with endergonic photocatalysis

Nature Reviews Chemistry volume 6, pages 745–755 (2022)Cite this article

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Abstract

Endergonic photocatalysis is the use of light to perform catalytic reactions that are thermodynamically unfavourable. While photocatalysis has become a powerful tool in facilitating chemical transformations, the light-energy efficiency of these processes has not gathered much attention. Exergonic photocatalysis does not take full advantage of the light energy input, producing low-energy products and heat, whereas endergonic photocatalysis incorporates a portion of the photon energy into the reaction, yielding products that are higher in free energy than the reactants. Such processes can enable catalytic, atom-economic syntheses of reactive compounds from bench-stable materials. With respect to environmental friendliness and carbon neutrality, endergonic photocatalysis is also of interest to large-scale industrial manufacturing, where better energy efficiency, less waste and value addition are highly sought. We therefore assess here the thermochemistry of several classes of reported photocatalytic transformations to showcase current advances in endergonic photocatalysis and point to their industrial potential.

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Fig. 1: Graphical representations of typical free-energy profiles for reactions.
Fig. 2: Deracemization and ring-opening isomerization.
Fig. 3: Olefin isomerization reactions.
Fig. 4: Dearomatization and cycloaddition reactions.
Fig. 5: Dehydrogenations and dehydrogenative cross-couplings.
Fig. 6: Group transfer reactions.

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Acknowledgements

We thank the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation; grant TRR 325-444632635) for funding support. H.W. thanks N. Y. Shin (Princeton University) for a discussion regarding deracemization.

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

    Huaiju Wang, Ya-Ming Tian & Burkhard König

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  1. Huaiju Wang
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All authors contributed to the conception and writing process of the manuscript. H.W. performed the computational studies.

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Correspondence to Burkhard König.

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Wang, H., Tian, YM. & König, B. Energy- and atom-efficient chemical synthesis with endergonic photocatalysis. Nat Rev Chem 6, 745–755 (2022). https://doi.org/10.1038/s41570-022-00421-6

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