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Asymmetric photoredox catalytic formal de Mayo reaction enabled by sensitization-initiated electron transfer

Nature Chemistry (2024)Cite this article

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Abstract

Visible-light-driven photoredox catalysis is known to be a powerful tool for organic synthesis. Its occurrence critically depends on the twice exothermic single-electron transfer processes of photosensitizers, which are governed by the redox properties of the species involved. Hence, the inherently narrow range of redox potentials of photosensitizers inevitably constrains their further availability. Sensitization-initiated electron transfer has recently been found to effectively overcome this substantial challenge. However, feasible and practical strategies for designing such complicated catalytic systems are rather scarce. Herein we report an elaborate dual-catalyst platform, with dicyanopyrazine as a visible light photosensitizer and a pyrenyl-incorporated chiral phosphoric acid as a co-sensitizer, and we demonstrate the applicability of this sensitization-initiated electron transfer strategy in an asymmetric formal de Mayo-type reaction. The catalysis platform enables otherwise thermodynamically unfavourable electron transfer processes to close the redox cycle and allows for precise access to valuable enantioenriched 1,5-diketones with a wide substrate range.

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Fig. 1: Background, concept, motivation and design of the present work.
Fig. 2: Optimization of the reaction conditions.
Fig. 3: Synthetic applications and mechanistic studies.

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Data availability

The authors declare that all data supporting the findings of this study are available in the paper and its Supplementary Information. Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2234002 (97), 2234003 (98), 2234004 (31), 2234005 (59), 2234006 (93), 2234007 (SX19168) and 2234008 (SX19171). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/.

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Acknowledgements

This work was financially supported by the National Science Foundation of China (21925103 and 22171072), Henan University and Henan Normal University.

Author information

Authors and Affiliations

  1. Key Laboratory of Natural Medicine and Immuno-Engineering of Henan Province, Henan University, Kaifeng, P. R. China

    Xin Sun, Xu Ban, Xiaowei Zhao & Zhiyong Jiang

  2. School of Chemistry and Chemical Engineering, Pingyuan Laboratory, Henan Normal University, Xinxiang, P. R. China

    Yilin Liu, Yanli Yin & Zhiyong Jiang

  3. College of Advanced Interdisciplinary Science and Technology, Henan University of Technology, Zhengzhou, P. R. China

    Yanli Yin

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Contributions

Z.J. and X.S. conceived and designed the experiments. X.S. and Y.L. performed the experiments. X.S., Y.Y., X.Z. and X.B. analysed and interpreted the results. X.S., X.B. and Z.J. prepared the Supplementary Information. Z.J. and X.B. wrote the paper. All authors discussed the results and commented on the paper.

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Correspondence to Zhiyong Jiang.

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Competing interests

The authors declare no competing interests.

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Peer review information

Nature Chemistry thanks Christoph Kerzig and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

General information, general experimental procedures, synthetic applications, mechanistic studies, determination of the absolute configurations, characterization of adducts, copies of NMR spectra and references.

Supplementary Data 1

Crystallographic data for compound 97; CCDC reference 2234002.

Supplementary Data 2

Crystallographic data for compound 98; CCDC reference 2234003.

Supplementary Data 3

Crystallographic data for compound 31; CCDC reference 2234004.

Supplementary Data 4

Crystallographic data for compound 59; CCDC reference 2234005.

Supplementary Data 5

Crystallographic data for compound 93; CCDC reference 2234006.

Supplementary Data 6

Crystallographic data for compound SX19168 derived from product 73; CCDC reference 2234007.

Supplementary Data 7

Crystallographic data for compound SX19171 derived from product 89; CCDC reference 2234008.

Supplementary Data 8

Structure factors for compound 97; CCDC reference 2234002.

Supplementary Data 9

Structure factors for compound 98; CCDC reference 2234003.

Supplementary Data 10

Structure factors for compound 31; CCDC reference 2234004.

Supplementary Data 11

Structure factors for compound 59; CCDC reference 2234005.

Supplementary Data 12

Structure factors for compound 93; CCDC reference 2234006.

Supplementary Data 13

Structure factors for compound SX19168 derived from product 73; CCDC reference 2234007.

Supplementary Data 14

Structure factors for compound SX19171 derived from product 89; CCDC reference 2234008.

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Sun, X., Liu, Y., Yin, Y. et al. Asymmetric photoredox catalytic formal de Mayo reaction enabled by sensitization-initiated electron transfer. Nat. Chem. (2024). https://doi.org/10.1038/s41557-024-01502-3

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