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Dicarboxylation of alkenes, allenes and (hetero)arenes with CO2 via visible-light photoredox catalysis

Nature Catalysis volume 4, pages 304–311 (2021)Cite this article

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Abstract

Light-driven utilization of CO2 in organic synthesis is highly attractive because it mimics nature. However, such transformations are mainly limited to the incorporation of only a single CO2 molecule into organic compounds, far less than the number of CO2 molecules fixed in the product in photosynthesis. Here we report the visible-light photoredox-catalysed dicarboxylation of alkenes, allenes and (hetero)arenes with the incorporation of two CO2 molecules. This method realizes the formation of multiple C–C bonds with high chemo- and diastereoselectivities under mild conditions, which represents a simple, rapid and sustainable approach to valuable dicarboxylic acids. Moreover, this transition-metal-free protocol exhibits a low catalyst loading, good functional group tolerance, broad substrate scope, facile scalability and easy product derivatizations to give drug and material molecules. Mechanistic studies indicate a pathway by which a visible-light-induced two-electron reduction via sequential single electron transfer generates radical anions of such unsaturated substrates, broadening the repertoire of strategies.

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Fig. 1: Difunctionalization of alkenes via visible-light photoredox catalysis.
Fig. 2: Screening the reaction conditions.
Fig. 3: Substrate scope of 1,1-diarylethylenes, monoarylethylenes and acrylates.
Fig. 4: Substrate scope of allenes and 1,3-dienes.
Fig. 5: Substrate scope of polycyclic aromatic hydrocarbon.
Fig. 6: Investigation of the mechanism.
Fig. 7
Fig. 8: Gram-scale reaction and product diversification.

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Data availability

Details about materials and methods, experimental procedures, mechanistic studies, characterization data and NMR spectra are available in the Supplementary Information. Additional data are available from the corresponding author upon reasonable request. Crystallographic data are available from the Cambridge Crystallographic Data Centre with the following codes: (E)-2aw (CCDC 1922731), cis-8a-Me (CCDC 1956271) and trans-8k′-Me (CCDC 1968028), These data can be obtained free of charge from www.ccdc.cam.ac.uk/data_request/cif.

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Acknowledgements

We thank S. Ma and H. Qian (Fudan University) for their samples of allenes, valuable discussion and suggestions. We also thank R. Martin (ICIQ) and J. J. Chruma (Sichuan University) for valuable discussion and help. Financial support was provided by the National Natural Science Foundation of China (21822108, 21772129), the Fok Ying Tung Education Foundation (161013), Sichuan Science and Technology Program (20CXTD0112), Beijing National Laboratory for Molecular Sciences (BNLMS201903), Fundamental Research Funds from Sichuan University (2020SCUNL102), and the Fundamental Research Funds for the Central Universities. We also thank X. Wang from the Analysis and Testing Center of Sichuan University and the comprehensive training platform of the Specialized Laboratory in the College of Chemistry at Sichuan University for compound testing.

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Authors and Affiliations

  1. Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu, P. R. China

    Tao Ju, Yu-Qin Zhou, Ke-Gong Cao, Qiang Fu, Jian-Heng Ye, Guo-Quan Sun, Li-Li Liao & Da-Gang Yu

  2. The Collaborative Innovation Center for Eco-Friendly and Fire-Safety Polymeric Materials, National Engineering Laboratory of Eco-Friendly Polymeric Materials (Sichuan), College of Chemistry, Sichuan University, Chengdu, P. R. China

    Xiao-Feng Liu & Li Chen

  3. Beijing National Laboratory for Molecular Sciences, Beijing, P. R. China

    Da-Gang Yu

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Contributions

D.-G.Y. and T.J. conceived and designed the study, and wrote the paper. T.J., Y.-Q.Z., K.-G.C., Q.F., J.-H.Y., G.-Q.S., X.-F.L., L.C. and L.-L.L. performed the experiments and mechanistic studies. T.J. performed the crystallographic studies. All the authors contributed to the analysis and interpretation of the data.

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Correspondence to Da-Gang Yu.

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A patent on this work has been filed in China under patent application number 201910319124.9.

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Peer review information Nature Catalysis thanks the anonymous reviewers for their contribution to the peer review of this work.

Supplementary information

Supplementary Information

Supplementary Methods, References, Figs. 1–12 and Tables 1–5.

Supplementary Data 1

Crystallographic Data of compound (E)-2aw.cif.

Supplementary Data 2

Crystallographic Data of compound cis-8a-Me.ci.f

Supplementary Data 3

Crystallographic Data of compound trans-8k’-Me.cif.

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Ju, T., Zhou, YQ., Cao, KG. et al. Dicarboxylation of alkenes, allenes and (hetero)arenes with CO2 via visible-light photoredox catalysis. Nat Catal 4, 304–311 (2021). https://doi.org/10.1038/s41929-021-00594-1

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