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Metallaphotoredox-enabled aminocarboxylation of alkenes with CO2

Nature Catalysis volume 6, pages 959–968 (2023)Cite this article

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Abstract

The conversion of CO2 to valuable chemicals is highly desirable for sustainable development. Among the various methods available, the difunctionalizing carboxylation of alkenes with CO2 emerges as an exceptionally efficient approach that facilitates the rapid construction of complex carboxylic acids and derivatives. However, existing systems have been limited to monocatalytic strategies and a few specific reaction types. Here we report a synergistic strategy to realize the aminocarboxylation of alkenes with CO2, providing efficient and practical synthetic access to valuable β-amino acids. The pivotal role of binaphthol as a photocatalyst in photoredox catalysis is demonstrated, enabling the single-electron activation of alkenes, generating radical anion intermediates. The remarkable aspect of this strategy lies in the efficient merger of photocatalysis and copper catalysis, enabling the rare orthogonal difunctionalization of alkene radical anions under redox-neutral conditions. Moreover, this strategy features mild conditions, high and unique selectivities, good functional group tolerance, facile product derivations and generality in realizing the hydroamination of alkenes.

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Fig. 1: Strategies for the 1,2-difunctionalizing carboxylation of alkenes with CO2.
Fig. 2: Screening the reaction conditions.
Fig. 3: Substrate scope of amines.
Fig. 4: Substrate scope of alkenes.
Fig. 5: Investigation of the mechanism.
Fig. 6: Synthetic applications and generality of this strategy.

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Data availability

Details about the 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

Financial support is provided by the National Natural Science Foundation of China (22225106; to D.-G.Y.), Fundamental Research Funds from Sichuan University (2020SCUNL102; to D.-G.Y.) and the Fundamental Research Funds for the Central Universities. We also thank X. Wang from the Analysis and Testing Center of Sichuan University as well as J. Li, Q. Zhang and D. Deng from 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, People’s Republic of China

    Jun-Ping Yue, Jin-Cheng Xu, Hai-Tian Luo, Xiao-Wang Chen, He-Xin Song, Yu Deng, Lihua Yuan, Jian-Heng Ye & Da-Gang Yu

  2. State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin, People’s Republic of China

    Da-Gang Yu

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Contributions

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

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Correspondence to Jian-Heng Ye or Da-Gang Yu.

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The authors declare the following competing financial interest(s): a Chinese patent on this work has been applied with the number 202211731369.0 (D.-G.Y., J.-P.Y., J.-C.X., H.-T.L., H.-X.S., Y.D., X.-W.C. and J.-H.Y.).

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Supplementary Methods, Tables 1 and 2, Figs. 1–16 and refs. 1–22.

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Yue, JP., Xu, JC., Luo, HT. et al. Metallaphotoredox-enabled aminocarboxylation of alkenes with CO2. Nat Catal 6, 959–968 (2023). https://doi.org/10.1038/s41929-023-01029-9

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