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Visible-light photocatalytic di- and hydro-carboxylation of unactivated alkenes with CO2

Abstract

High value utilization of carbon dioxide (CO2) has attracted worldwide attention for decades. Catalytic carboxylation of alkenes with CO2 to synthesize valuable carboxylic acids and diacids is highly important. Although visible-light photocatalytic single-electron transfer reduction of CO2 could provide an alternative choice for diverse chemo- and regio-selectivities, it has rarely been investigated in carboxylation. Moreover, visible-light photocatalytic carboxylation of unactivated alkenes with CO2•− has never been reported. Here we report visible-light photocatalytic di- and hydro-carboxylation of unactivated alkenes with CO2. In contrast to previous reports limited to activated alkenes, diverse unactivated aliphatic alkenes undergo selective carboxylations to give carboxylic acids, dicarboxylic acids and unnatural α-amino acid derivatives in moderate to good yields. Mechanistic studies suggest that CO2 might be reduced to CO2•− via consecutive photo-induced electron transfer, and this species would attack unactivated alkenes followed by subsequent hydrogen atom transfer and other relevant processes to afford the corresponding products.

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Fig. 1: Visible-light photocatalytic carboxylation of alkenes with CO2.
Fig. 2: Substrate scope for the reductive dicarboxylation.
Fig. 3: Substrate scope for the hydrocarboxylation via intermolecular HAT.
Fig. 4: Control experiments.

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.

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Acknowledgements

We thank O. S. Wenger, F. Glaser and B. Pfund from the University of Basel and J. J. Chruma from the University of Virginia for valuable suggestions. Financial support is provided by the National Natural Science Foundation of China (22225106, 21822108), Sichuan Science and Technology Program (20CXTD0112), Central Government Funds of Guiding Local Scientific and Technological Development for Sichuan Province (2021ZYD0063), Fundamental Research Funds from Sichuan University (2020SCUNL102) and the Fundamental Research Funds for the Central Universities. We also thank X. Wang, H. Chen and Y. Luo from the Analysis and Testing Center of Sichuan University as well as J. Li, Q.-F. Zhang, D. Deng, L. Wei and Y. Long from the College of Chemistry at Sichuan University for analytic testing and valuable help.

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D.-G.Y. conceived, designed and supervised the study. L.S., W.W. and D.-G.Y. wrote the paper. L.S., W.W., J.-P.Y., Y.-X.J., M.-K.W., H.-P.Z., S.-S.Y. and L.-L.L. performed the experiments and mechanistic studies. L.S. and W.W. contributed equally to this work. All authors contributed to the analysis and interpretation of the data.

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Correspondence to Da-Gang Yu.

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The authors declare the following competing financial interest(s): two Chinese Patents on this work have been applied for with the numbers 202111106015.2 (D.-G.Y., L.S., M.-K.W. and Y.-X.J.) and 202210530049.2 (D.-G.Y., W.W., J.-P.Y., L.S., H.-P.Z., S.-S.Y. and L.-L.L.).

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Song, L., Wang, W., Yue, JP. et al. Visible-light photocatalytic di- and hydro-carboxylation of unactivated alkenes with CO2. Nat Catal 5, 832–838 (2022). https://doi.org/10.1038/s41929-022-00841-z

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